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Review

Cite This: Chem. Rev. XXXX, XXX, XXX-XXX pubs.acs.org/CR

Photochemistry and Photophysics in Silica-Based Materials: Ultrafast

and Single Molecule Spectroscopy Observation
Noemí Alarcos,† Boiko Cohen,† Marcin Ziółek,‡ and Abderrazzak Douhal*,†
†
Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La
Mancha, Avenida Carlos III, S.N., 45071 Toledo, Spain
‡
Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland

ABSTRACT: Silica-based materials (SBMs) are widely used in catalysis, photonics, and
drug delivery. Their pores and cavities act as hosts of diverse guests ranging from
classical dyes to drugs and quantum dots, allowing changes in the photochemical
behavior of the confined guests. The heterogeneity of the guest populations as well as
the confinement provided by these hosts affect the behavior of the formed hybrid
materials. As a consequence, the observed reaction dynamics becomes significantly
different and complex. Studying their photobehavior requires advanced laser-based
spectroscopy and microscopy techniques as well as computational methods. Thanks to
the development of ultrafast (spectroscopy and imaging) tools, we are witnessing an
increasing interest of the scientific community to explore the intimate photobehavior of
these composites. Here, we review the recent theoretical and ultrafast experimental
studies of their photodynamics and discuss the results in comparison to those in
homogeneous media. The discussion of the confined dynamics includes solvation and
intra- and intermolecular proton-, electron-, and energy transfer events of the guest
within the SBMs. Several examples of applications in photocatalysis, (photo)sensors, photonics, photovoltaics, and drug delivery
demonstrate the vast potential of the SBMs in modern science and technology.

CONTENTS 3.3.2. Energy Transfer in Dye-Doped Mesopo-

rous Materials AF
1. Introduction B 3.3.3. Donor/Acceptor Concentration Effects
2. Theoretical Studies D on Energy Transfer AI
2.1. Solvation in Silica-Based Materials E 3.3.4. Energy Transfer in Silica-Coated Quan-
2.1.1. Water and Silica Materials E tum Dots and Metal Nanoparticles AJ
2.1.2. Other Solvents and Silica Materials F 3.4. Homo-Energy Transfer and Aggregates
2.1.3. Impact on Solvation Dynamics G Formation AL
2.2. Photoinduced Processes in Trapped Mono- 4. Single Molecule AP
mers and Aggregates I 4.1. Single Molecule Reactivity in Silica-Based
2.2.1. Impact of SBMs on Absorption and Materials AQ
Emission Spectra of Chromophores I 4.2. Single Molecule Diffusion in Silica-Based
2.2.2. Impact on Excited-State Dynamics J Materials AR
2.2.3. Impact of Guest Aggregation K 4.3. Other Studies AR
3. Ensemble Average Time-Resolved Studies of 4.4. Electronic Nanoconfinement AS
Photoinduced Processes in Silica-Based Materials L 5. Recent Applications of Silica-Based Materials AT
3.1. Proton-Transfer Reactions L 5.1. Photocatalysis AT
3.1.1. Intermolecular Proton-Transfer Pro- 5.2. Photonics AY
cesses M 5.2.1. Sensors BA
3.1.2. Intramolecular Proton-Transfer Reac- 5.3. Photovoltaics BE
tions S 5.4. Drug Delivery BG
3.2. Electron-Transfer Reactions U 6. General Conclusion and Outlook BJ
3.2.1. Intramolecular Charge-Transfer Reac- Author Information BK
tions V Corresponding Author BK
3.2.2. Intermolecular Electron-Transfer Reac- ORCID BK
tions AA
3.3. Energy-Transfer Events AD
3.3.1. Energy Transfer in Dye-Doped Zeolites AE
Received: July 13, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.chemrev.7b00422

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Scheme 1. Frameworks of the Silica-Based Materials (SBMs) Used in the Studies Commented in This Reviewa
a
(A) and (B) show the microporous and mesoporous hosts, respectively.
Notes
Biographies
Acknowledgments
Dedication
Abbreviations
General Abbreviations
Symbols and Rate Constants
Material Structures
Molecules
References
1. INTRODUCTION
Silica-based materials (SBMs) are one of the most studied
framework systems in advanced chemical and biological
applications, being used in catalysis, photonics, and drug
delivery. They act as hosts for diverse organic molecules (dyes
and drugs for example), allowing changes in the photochemical
behavior of the confined guests. The formed composites show a
variety of photophysical and photochemical events that could
be used to develop smart devices, such as drug nanocarriers,
nanosensors, nanoOLEDs, nanolasers, energy storage nano-
space, and nanophotocatalysts.
Several review articles on the structural properties of SBMs
and their composites with different chromophores have been
published.1−17 However, these works have not been oriented
toward the photodynamics in the formed composites. They
rather focus on the photochemistry at long time scale
(nanosecond-millisecond regime). Therefore, a great knowl-
edge on slow photochemical events and stability of the formed
photoproducts has been reached and used for some application
purposes.3,5,13−15,18−28 More than two decades ago, ultrafast
laser-based techniques allowed one to witness the chemical
bond and electronic events in real-time of reactions.29,30 These
techniques are being used to characterize the molecular events
in condensed phase, providing details on solvation, electron,
proton, and energy transfer events. 16,27,31−43 Confining
molecules within chemical and biological cavities leads to
Review
BK guest dynamics and spectroscopy different from those in
BK solutions.2,7,44−49
BK In recent years, many studies of ensemble average ultrafast
BK (femtosecond regime) processes within the confined space
BK provided by the nanochannels and nanocavities of the zeolite
BK and mesoporous materials have been published. However, the
BL most recent systematic review of photodynamical studies using
BL SBM composites was published in 2003.4 Thus, there is a
BM strong need for a detailed review of the recent contributions on
BN the photoinduced fast and ultrafast dynamical properties of
such SBMs interacting with chromophores and drugs. Here, by
fast and ultrafast dynamics we mean events happening in pico-
and femtosecond (ps-fs) regimes. The present review mainly
focuses on contributions since 2005. However, in a few places,
earlier relevant contributions are also presented. We also review
recent works using time-resolved fluorescence microscopy
applied to SBM composites. From the point of view of the
framework materials, our interest is focused on microporous
silica and aluminosilica sieves (e.g., zeolites), mesoporous silica
sieves (e.g., MCM41, SBA15), silica nanoparticles, and silica
shells. Scheme 1 shows the framework of these SBMs confining
media, which have been used in the published works
commented in this review. As for the encapsulated
chromophores, the main part is devoted to organic molecules,
but quantum dots (QDs), metal nanoparticles, and perovskites
are also presented. The chemical structure of these guests is
shown in Schemes 2−8.
Theoretical studies of the photophysical and photochemical
processes in silica-based composites are, without doubt, much
more difficult in comparison to the calculations of isolated
molecules or even those in a homogeneous environment.
Caution must be taken when interpreting the results, due to the
use of more approximated methods or base sets. Similarly, time-
resolved experiments in such hybrid systems become a
challenge against conventional studies in solutions because of
their more complex and less repeatable samples preparation,
difficulties in successful measurements (e.g., studies in solid
state or in suspensions where the light is severely scattered),
B DOI: 10.1021/acs.chemrev.7b00422
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Chemical Reviews
Scheme 2. Molecular Structures of the Compounds Interacting with SBMs and Discussed in the Theoretical Section 2
and often a more complicated data analysis. We believe that the
time of ultrafast studies of simple molecular systems dissolved
in solutions is passing. Such systematic studies in the past 30
years resulted in profound knowledge about the photophysical
processes that occur in solutions on the time scales of
femtoseconds (fs), picoseconds (ps), and nanoseconds (ns).
The rapid increase in novel technologies requires the scientists
to focus more on systems that are application-oriented,
including the composites formed by chromophores in SBMs.
The basic studies of novel chromophores in solutions are still
necessary (e.g., to get to know the effects of surrounding
polarity, viscosity, pH, and specific interactions) but rather as
references to investigate more complex environments. With the
recent development of turn-key ultrafast laser systems of high
stability, and commercially available time-resolved spectrom-
eters (e.g., transient absorption in UV, visible, NIR ranges, up-
conversion, time-correlated single-photon counting (TCSPC),
C DOI: 10.1021/acs.chemrev.7b00422
Review
streak-cameras, and fluorescence microscopy), the possibility of
studying complex systems without having a detailed knowledge
in ultrafast laser physics is growing. An analogous situation
happens in the field of theoretical calculations, where the rapid
development of computational tools has empowered the field in
the two last decades.
In addition to the Introduction and Conclusion, this review
contains four sections. The review is organized as follows: the
subsequent section (section 2) is devoted to the theoretical
studies. Its first section 2.1 examines the ultrafast dynamics of
water and other solvents within the pores and cages provided
by the SBMs, the solvation effects on the solutes, and its impact
on the observed dynamics and spectroscopy. The second
section of the theoretical part (section 2.2) presents the studies
of the electronic coupling between the guest and the framework
of the host and its relevance to the photobehavior of the
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formed composites. The effects of aggregation and energy
transfer between closely laying guests are also considered.
Section 3 (ensemble average time-resolved studies of
photoinduced processes in SBMs) is the main and the longest
section of the review, presenting and discussing the recent
reports on the dynamics and spectroscopy of different
photoinduced processes taking place within silica-based hosts
on the time scale from fs to ns. Section 3.1 deals with the
excited-state proton-transfer reactions that can be either intra
or intermolecular in nature. We review the effects that the
silica-based hosts have on these processes. The framework of
the host can affect directly or indirectly the excited-state
proton-transfer reactions by modifying the electronic distribu-
tion within the guest and, thus, altering its dynamics and
subsequent events. In specific cases, the framework can act as a
proton acceptor/donor, inducing an intermolecular proton-
transfer reaction within the composites. The effects of the pore
size, metal doping, and functionalization of the host on the
proton-transfer event of the guest are also discussed. Section
3.2 is devoted to electron-transfer reactions (one of the most
important reactions in nature), and it includes both the passive
and active role of the host. For the first case, the host
frameworks can affect the charge separated (CS) states of the
encapsulated guest, together with the rate constants of intra-
and intermolecular charge transfer reactions, and the nano-
solvation dynamics. As for the active role, framework
modification using metal doping functionalization or pore size
can further affect the charge separation (within the guest) and
can even facilitate electron injection to the doping metal. We
also examine the effects of specific and nonspecific interactions
between the guest and the host on the electron-transfer events.
SBMs are one of the most suitable hosts to build multi-
chromophoric scaffolds for energy transfer, and the related
reports dedicated to understanding these events and developing
multichromophoric and hybrid systems by functionalization,
doping, and pore size modification are commented on in
section 3.3. The effects of energy donor and acceptor
concentrations in the nanohosts on the processes in silica-
coated QDs and metal nanoparticles are considered as well.
Finally, section 3.4 analyzes the results from the point of view
of molecular aggregates formation. The limited space of the
nanochannels and nanocavities of the zeolites and mesoporous
materials creates physical conditions for strong intermolecular
interactions between the encapsulated guest molecules, thus
giving rise to H- and J-aggregates of the caged monomers. We
discuss how this type of guest−guest interactions shapes the
photophysical behavior of the composites, and how doping and
functionalization of the host can affect the distribution of the
aggregates and interacting monomers.
Section 4 of the review shows the most recent studies
oriented toward using the photophysical properties of the
guests to characterize the hybrid complexes at single molecule/
particle level. Knowing the interaction of fluorescent dyes with
the silica-based host framework is paramount to deciphering
the distribution of the guests and the type of specific and
nonspecific interactions in the composites, by passing the
ensemble average limitations. Special attention is paid to the
electronic nanoconfinement, reflecting the effect of the host
framework on the photophysical properties of the guest from
the point of view of orbitals coupling. Section 5 summarizes the
most relevant applications of SBM composites that are related
to the photophysical and photochemical processes presented in
sections 2−4. Thus, we focused on the applications using light
D DOI: 10.1021/acs.chemrev.7b00422
Review
in areas such as photocatalysis, photonics, sensors, photo-
voltaics, and drug delivery. A few results of ns−ms
luminescence (that were not presented in parts 3−4) related
to application-oriented studies are also commented in section 5.
The review ends with the conclusions that can be drawn on the
basis of the photophysical processes within SBMs, and we
address future challenges and the possibility of how to face
them.
The goal that this review, among others, is to provide a guide
of general changes in the photodynamics (with respect to
homogeneous solvents) that one can expect when considering a
given chromophore interacting with silica-based hosts and
nanostructures. For example, excited guests, which have a
significant change in their dipole moments, should exhibit
slower solvation (nanosolvation) with respect to that in
solutions, and the extent of this slowing down depends on
their position and adsoption on the silica pores and framework
governing the specific and nonspecific interactions in the
composites. When the guest nonradiative deactivation depends
on its internal rotation or twisting, we anticipate that its
fluorescence lifetime in the composite will increase as a result of
restriction in motion. On the other hand, other processes can
make the photodynamics faster in SBMs than those in
solutions. Excited state lifetime might become shorter due to
self-quenching (homo energy transfer) upon high dye loading
in the pores, and the size of host pores might favor or disfavor
aggregates formation. On the other hand, metal doping of silica
materials can trigger additional deactivation channels, due to
charge transfer (e.g., electron injection). Small modifications in
acidity or basicity inside silica pores might influence the proton-
transfer reaction rates and promote the deactivation route at
the expense of another one. Often, it may even lead to the
occurrence of a new molecular form (e.g., radical anions,
cations, and CS state) in the ground state, which drastically
changes the overall photophysics and photochemistry of the
confined system. These are the most common and simplest
examples, with much more details, special cases, and competing
factors outlined in the following parts.
Our review of the fs−ps time-resolved studies of the
photoinduced processes taking place in the hybrid SBM
complexes should give a concise perspective on the clues and
knowledge of the challenges found in the photocharacterization
of these composites. One of its goals is to trigger further
research to advance in the related subfields and emerge with
others in science and technology. We hope that the review will
be of great interest to a wide scientific community (in
chemistry, nanomaterials, spectroscopy, physics, nanomedicine,
and pharmacology) that will benefit from having at hand the
state-of-the-art in the ultrafast photodynamics within silica-
based composites, encouraging more and more scientific groups
to join this fascinating and promising field to boost the
knowledge opening doors for new smart applications of SBM
composites.
2. THEORETICAL STUDIES
There is a strong discrepancy between the number of
theoretical and experimental works that examine ultrafast
photoinduced processes in silica-based materials (SBMs). To
predict the behavior of the system after light absorption, the
interaction of the excited state of the organic molecules with
silica-based structures must be optimized, which is difficult not
only because of the large systems that are involved but also due
to the lack of proper methodology, which is still being
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developed (even in the case of small molecules). Another
problem is the verification of the calculated results: the
calculations are usually performed on small molecules, while
the experiments, involving dyes on SBMs, are usually
performed with large molecules possessing the desired
properties and generating strong enough signals to analyze
(e.g., high extinction coefficient in the visible range, strong
dipole moment changes upon excitation, etc.).
Compared with the case just described, there are relatively
many theoretical reports that address ground-state interactions
and adsorption of gases and small liquid molecules on SBMs.
These studies, particularly relevant to catalysis, have been
recently reviewed.15 Another area of theoretical studies of
adsorption and diffusion of small molecules in mesoporous
silica is devoted to sensing application (see section 5). For
example, a physico-mathematical model for the related kinetics
was recently proposed to predict the kinetic behavior of the
explosive trinitrotoluene (TNT) in mesoporous films.50 On the
contrary, studying the adsorption of large biomolecules is
important in, for example, drug delivery (see section 5). Such
calculations have been recently commented on.11 The above
reviews also outlined the main theoretical methods that are
used to get the structures of SBMs and their interactions with
the organic guest molecules.11,15 Therefore, these subjects will
not be considered in this review. Below, we mainly focus on the
theoretical works that are dedicated to ultrafast and fast
dynamics in SBMs and the properties of the nanoconfined
molecules in their excited states or, at least, those that predict
their stationary absorption and emission spectra. The first
section is devoted to solvation dynamics that influences the
relaxation of the excited states of the dyes. In the second
section, the direct interaction of the dyes with SBMs will be
considered with regards to photoinduced processes.
2.1. Solvation in Silica-Based Materials
Solvation dynamics is determined by the ability of solvent
molecules to reorganize around a chromophore, thereby
minimizing the energy of the resulting solvent−solute entity.
The typical and most frequently used way to study solvation
dynamics is the electronic excitation of a molecule and gating
its fluorescence signal at short and different times after its
excitation. A suitable chromophore should have different dipole
moments in the ground and excited states in a polar solvent. If
the electronically first excited state (S1) has significant
intramolecular charge transfer (ICT) character, solvent
molecules around the solute move and rotate to assume the
energetically optimum position. The stabilization of the excited
solute in the new electronic configuration is then accompanied
by a redshift in its fluorescence spectra (Stokes shift). This shift
with the gating time is analyzed to get solvation time dynamics.
2.1.1. Water and Silica Materials. An important result
from the studies of solvation dynamics is predicting the
interactions of solvent molecules with SBMs, particularly in
materials in which nanoconfinement occurs. Such studies will
be briefly discussed below, while the experimental findings are
presented in section 3.2.1. Not surprisingly, water is the most
frequently theoretically studied solvent because of its simple
molecular structure, well-known strong interactions with SBMs,
and relevance in biology and medicine, and to our life.
Advances in the field using theoretical tools were reviewed in
2011.33 Different models describing the dynamical behavior of
solvent molecules in confined structures were summarized
there. The simplest model (the so-called two-state or core−
E DOI: 10.1021/acs.chemrev.7b00422
Review
shell model) divides solvent (water) molecules into two
groups: (1) bound (surface) and (2) free (bulk) water. Surface,
or shell, molecules are assumed to have significantly modified
properties due to their direct interaction with silica and their
immobilization on its surface via H-bonding. In contrast, core
molecules distant from the interface are considered to have
bulklike properties. A given property of a confined liquid
should scale as 1/R and 1/R2 in cylindrical and spherical
confinements, respectively, due to the populations of the
molecules in the bound and free states (R is the radius of the
confining space). A more complex model assumes that the
influence of the interface extends further and more smoothly
into the liquid than the step function used in a two-state model
describes. A dynamic exchange model attributes the long-time
dynamics to the exchange of bound and free water (a bound
water molecule can only take part in solvation dynamics by
exchanging with a free water molecule). This model leads to the
prediction of a temperature dependence of the solvation
dynamics that is due to an activation energy caused by a free
energy barrier. This barrier is generated by the H-bonding
character of water molecules with the silica surface. Finally, a
model with chromophore diffusion assumes that changes occur
in the position of the solute molecule when its dipole moment
changes (excitation). We will discuss this model in the next
section.
More recently, the reorientation dynamics of water in
nanoscale hydrophilic or hydrophobic silica pores were
investigated using molecular dynamics simulations.51 The
reorientation of water in hydrophilic confinement occurs in
more than one nanosecond (2 orders of magnitude longer than
in bulk water) and exhibits a power-law decay. The hydro-
phobic pores (simulated as silica with no charges) affect more
modestly the dynamics, making water molecules reorientation
only 2.5 times slower than that in the bulk. Moreover, the
power-law decay of the correlation function in the hydrophilic
pores was explained in terms of heterogeneity of the surface
and demonstrates the incompleteness of the two-state model.
The H-bond jump model was used to study the heterogeneity
where H-bond acceptors on the pore surface (bridging oxygens
or silanols) exchange H-bonding interactions with water
molecules. This mechanism, when combined with the surface
roughness, leads to a distribution of jump times. Obviously,
water molecules cannot form H-bonds with the interface when
they are in the hydrophobic pores, and the reorientation
dynamics is governed only by the local excluded volume.
Molecular dynamics simulations combined with analytic
modeling were also used to explain why water reorientation
dynamics does not vary monotonically with the surface
hydrophilicity.52 The increasing hydrophilic character is
accompanied by two competing effects within the interfacial
layer. The first effect is a rearrangement of water molecules. In
this scenario, when the hydrophilicity of a surface increases, an
increasing fraction of water molecules point their OH groups
toward the surface. Further increases in hydrophilicity increases
the interaction energy, slowing down the reorientation times.
It is well-established that while fully hydroxylated surfaces
(surface density of 4−5 Si−OH groups per nm2) have a
hydrophilic character, highly dehydroxylated ones (approx-
imately 1−2 Si−OH per nm2) manifest a hydrophobic
character.11 The extended jump model in cases of hydrophilic
confinement was further studied by spatially resolving the H-
bond jump dynamics among individual sites on the silica pore
surface.53 The nonexponential dynamics was explained by a
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Chemical Reviews
Figure 1. Picture of the molecular dynamics of water in MCM41, after (A) 3.5 ps (potential energy equilibration reached) and (B) 6.5 ps. The water
shell (blue) is almost identical at both times. Reprinted with permission from ref 58. Copyright 2016 Royal Society of Chemistry.
broad distribution of rate constants for the exchange of H-
bonding partners, and the distribution was due to a variety of
local topographies at the silica surface. It was found that the key
factors that determine the distribution of jump types were
entropic: specifically, an excluded-volume effect for the
approach of a new partner and the elongation of the initial
H-bond. However, enthalpy effects arising from the chemical
heterogeneity of the pore surface contributed only weakly to
the distribution. The same research group investigated the
hydrophobic confinement in all-silica Linde type A (LTA)
zeolites.54 Water molecules reorientation was found to be
retarded by only a factor of 2−3 when compared with the bulk
values. The slowdown of water dynamics was more pronounced
at higher water loadings and was predominantly caused by an
excluded-volume effect (large fraction of water molecules lying
at the interface within the zeolite matrix). The authors
suggested that the presence of the interface and its chemical
nature have a much greater impact on water dynamics than
does the confinement.
Classical molecular dynamics simulations were used to study
the interaction of water with the external surface of silicalite-1.55
Despite the hydrophobic behavior of the silicalite structure and
the presence of hydrophilic OH groups on the surface, water
enters the zeolite pore system and forms a layer. The adsorbed
water molecules on this internal layer are H-bonded to each
other and to a layer of molecules that are adsorbed on the
surface and bound to the silanol groups. The surface layer has
an ordered structure with a thickness of approximately 7 Å.
The performed calculations were not only aimed at
explaining experimental findings but also predicting new results
and phenomena. Molecular dynamics calculations were recently
used to simulate the results of a two-dimensional infrared
spectroscopy (2D-IR) experiment, in which a novel ultrafast
technique probed the correlation and coherence times of the
molecular vibrations.56 The results predict that while the
frequency correlation of OH vibrations is nearly complete in
approximately 2 ps for bulk water, in a silica pore, this
correlation is significantly longer (6 ps). Moreover, the 2D
description of the distance of OH vibrations from the pore
surface drastically changed: there was little loss in the frequency
F DOI: 10.1021/acs.chemrev.7b00422
Review
correlation of the spectra at a distance of 2 Å, even until 1 ps.
While at a distance of 5 Å, the OH groups lose the memory of
their frequency much faster (although still slower than in the
bulk liquid). Therefore, the theoretical report shows that it
should be possible to probe the slower spectral diffusion of
confined water molecules (compared to the bulk liquid) by
performing and analyzing 2D-IR spectra.
Another recent work used density functional theory (DFT)
based-molecular dynamics simulations to study water interact-
ing with SBMs. Amorphous silica surfaces and quartz surfaces
were compared when they were in contact with water.57 It was
concluded that the water layer at the amorphous silica interface
is less dipolar than the one at the crystalline silica interface. The
layer of water molecules at the amorphous silica surface was
found to be immobile, and an adsorbed water molecule would
probably not be easily replaced by adsorbate organic molecules.
Other composite models at the DFT level with explicit solvent
water molecules were tested for the classical Mobil Catalytic
Materials of Number 41 (MCM41).58 Here, ab initio molecular
dynamics using an MCM41 channel having a silanol density of
5.8 Si−OH nm−2 showed that the first water layer is strongly
adsorbed on the silica wall (blue in Figure 1). The mobility of
the first shell of water is qualitatively very low, and water
molecules stay close to the channel surface and do not diffuse
during sampling times of up to 8 ps (Figure 1).
2.1.2. Other Solvents and Silica Materials. The
interaction of nonaqueous solvents with SBMs was also
theoretically studied. Molecular dynamics simulations of a
silica/acetonitrile interface were performed.59 Acetonitrile
molecules formed an arrangement at the silica surface that is
reminiscent of a lipid bilayer. Such a configuration is
considerably different from an antiparallel and dipole-paired
structure in the bulk liquid. It was also found that the silica
interface can affect the bulk liquid structure over a distance of
tens of angstroms. A similar bilayer structure was considered at
the interface between silica and propionitrile.60 However, the
CN vector of the cyanide group of propionitrile is more parallel
to the surface than that of acetonitrile. As a result, the
propionitrile bilayer is more compact and ordered than the
corresponding acetonitrile one (Figure 2A).
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Figure 2. (A) Comparison of the CN (vector of cyanine group) density (ρ) in acetonitrile and propionitrile (z is the center of the CN bond, ρB is
the bulk density. Reprinted from ref 60. Copyright 2012 American Chemical Society. (B) Number of hydrogen bonds per methanol molecule as a
function of distance from the silica surface and resultant polarity of the environment. Reprinted from ref 61. Copyright 2013 American Chemical
Society.

Figure 3. (A) Variation of free energy profiles, ΔA(x), and probability distributions, P(x), of a solute of different dipole moments: 5 D (black), 10 D
(blue), and 15 D (green) in the hydrophilic pore. The figure shows that the solute of a larger dipole moment (e.g., in the excited state) is located
further from the pore walls. Reprinted from ref 64. Copyright 2012 American Chemical Society. (B) A model system with a spherical solute in a
Lennard-Jones fluid confined between a slit of parallel walls at the distance H, below the solvation time obtained for solvophilic and solvophobic
walls (solute diameter is 3σ). Reprinted from ref 65. Copyright 2013 American Chemical Society.

Another theoretical report showed that the Coulombic
interaction of the π-electrons of benzene ring with the partial
charges carried by the silica atoms is of great importance in the
stability of the complex.62 The confined benzene exhibits
significant layering, and the rings of molecules close to the
interface tend to lie flat on the silica surface. The rotational
dynamics of this solvent in the center of the pore was found
slightly slower when compared to that of the bulk, with more
pronounced slowing in smaller pores. For example, the
reorientation time at 293 K was predicted to be ∼6 and ∼7
ps in nanopores with diameters of 3.6 and 2.0 nm, respectively,
while at the same temperature, this time was predicted ∼5 ps
for bulk benzene.
Molecular dynamics simulations were also used to character-
ize methanol.61 Strong H-bonds between the first layer of
methanol and the silanol groups of silica create a methyl-
terminated surface that results in a second layer having
significantly less density and H-bonds than the bulk solution
(Figure 2B). In agreement with the experimental findings, the
interfacial environment in this layer resembles to a nonpolar
solvent. Moreover, solvent reorientation times, in these first
two layers, are significantly slower than those observed in the
bulk solvent. Recently, replica exchange molecular dynamics
simulations were used to investigate the location of acetone and
G DOI: 10.1021/acs.chemrev.7b00422
methanol molecules that were dissolved in acetonitrile and
confined in nanoscale hydrophilic silica pores.63 Methanol
molecules with specific interactions were found to exist in two
distinct conformations that differ in their H-bonding states,
which resulted in two maxima in the position-dependent
densities of the molecules with respect to the distance from the
silica surface. Both entropy as well as H-bonding were found to
play important roles in determining the location and
orientation of the methanol molecules.
2.1.3. Impact on Solvation Dynamics. The configu-
rations of solvent molecules and their reorientation times that
are commented above have a direct effect on the solvation
dynamics of chromophores that interact with silica surfaces in
the presence of solvent. Experimental observations from time-
dependent fluorescence measurements (that were supported by
theoretical calculations) were divided into three groups: (i)
increase in solvation times observed in bulk solution, (ii)
appearance of new, longer times in the solvation dynamics, and
(iii) lack of any differences among the chromophores in bulk
solutions and those within silica structures.33 The used
chemical models (SBMs interacting with a solvent or a solute)
before 2010 that were proposed to explain the experimental
observations for nanoconfined silica structures have also been
summarized.33 It was argued that the chemical models with
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Chemical Reviews
Figure 4. (A) Coumarin 153 (C153) in methanol confined in different silica pores (from left to right: HOC, HIC, and RHOC). (B) Simulation of
changes in solvation-response function, S(t), with the time. The inset shows the unnormalized energy gaps, ΔE(t), which represents the environment
contribution (i.e., MeOH and pore walls), to the energy gap between the S1 and S0 Born−Oppenheimer potential energy surfaces of C153 at time t.
Reprinted from ref 67. Copyright 2011 American Chemical Society.
different solvent layers were insufficient to accurately reproduce
the experimental results, and that the effects of chromophore
diffusion upon excitation must be considered. This diffusion
occurs when the dipole moment of the chromophore increases
as a result of the electronic distribution changes from the
ground to the electronically excited state, and this diffusion
should be responsible for the long-time solvation dynamics. In
addition to that, the restriction of the solvent molecules to
move at the interface decreases its polarity relative to the host
interior. Therefore, the dependence of the location of a solute
molecule (guest) on its electronic charge distribution during
the time getting the photoresponse of the composite, and the
gradient in effective solvent polarity are likely important
features to take into account in understanding the behavior
of these systems.
The solute (guest) diffusion model has been further used. A
model molecule that was solvated by ethanol in a nanoscale
silica pore was examined as a function of its position (Figure
3A).64 The guest distribution depends on both its dipole
moment and its interaction with the surface of the silica pore,
which can be hydrophilic or hydrophobic in nature. The
electrostatic guest-pore interactions were responsible for the
shifts in the fluorescence spectrum of the guest molecules in
some locations near the hydrophilic wall. However, this effect
was absent when the guest is in the hydrophobic pore.
Therefore, while the guest-position distributions depend on its
dipole moment in both hydrophilic and hydrophobic pores, the
fluorescence spectra are only sensitive to the dye position in the
former case. As a result, time-dependent fluorescence measure-
ments of the hydrophobic pore system could be insufficient to
observe guest diffusion after excitation. However, the state-
dependent on its position might still have significant
importance in applications of porous materials.
The differences between hydrophilic and hydrophobic
confinement were also studied using another approach.65 The
authors generalized the case of water to any solvent, using the
terms of solvophilic and solvophobic probe. A substantial
slowing of solvation dynamics around a solute in strong
solvophilic confinement is due to the suppression of fluid
diffusion in the presence of the closely lying attractive walls, in
addition to restricted solvent dynamics. The solvation in strong
solvophobic confinement is slower than in the bulk but is not
slowed as significantly as in the solvophilic case (Figure 3B). In
this case, the effect was explained by the competition between
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restriction of solvent dynamics and faster in-plane solvent
diffusion.
More recently, studies of coumarin 153 (C153, Scheme 2) in
ethanol and confined in 2.4 nm hydrophilic amorphous silica
pore have been reported.66 At the ground state, the most likely
location of C153 when interacting with the SBMs is near the
pore surface, but two possible H-bonding structures lead to
different orientations. Internal energy and entropy competed
within the pore. The implication for solvation dynamics is that
the two calculated orientations might lead to diffusions of
different rates upon excitation. These differences in rates are
because the flat orientation of C153 has a larger effective
surface area (slower diffusion) to move into the interior than
the second, perpendicular orientation. In a subsequent work,
the positions of C153 in a hydroxyl-terminated silica pore
system was studied in both the ground and excited states.66 The
predicted movement of C153 toward the pore interior upon
excitation was attributed to more favorable nonspecific ethanol
solvation of the large dipole moment in the excited C153,
which occurred at the expense of H-bonding with the pore.
Interestingly, the free energy variations were calculated to be
comparatively small (1−3 kcal/mol), which suggests that
relatively modest changes in the confining framework or solute
interactions may generally have a significant impact on the
distribution of solute positions.
Solvation response functions of C153 were also simulated
from averages of non-equilibrium independent trajectories
obtained in molecular dynamic calculations.67 The investigated
solvent was methanol, and three kinds of silica pores were
examined (Figure 4A): hydrophobic cavities (HOC, in which
wall-solvent interactions were exclusively of the dispersive,
Lennard-Jones type), hydrophilic cavities (HIC, in which
unsaturated oxygen sites at the wall were transformed into OH
groups), and rugged pores (RHOC, in which 60% of the polar
groups were transformed into trimethylsilyl moieties). The
results of the simulation within the first 30 ps are presented in
Figure 4B. The overall responses were found to be between 2
and 4.5 times slower than the one observed in the bulk
methanol, the one associated with RHOC being the fastest
relaxation and the one corresponding to HIC the slowest.
Finally, the kinetic processes occurring on the ps−ns time
scale were also considered in the calculations of diffusion of
different molecules within SBMs. Molecular dynamics simu-
lations were performed and visualized on pure silica zeolite
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Chemical Reviews
silicalite MFI framework. The microporous zeolite contains two
channel systems that intersect tangentially, straight channels
and zigzag or sinusoidal channels. The diffusion dynamics were
simulated by modeling trapping in the subsequent cavities
separated by thermally activated jumps through the chan-
nels.68,69 These simulations were performed maintaining both
the framework flexibility and the realistic account of electro-
static interactions with adsorbed water. Two types of
adsorption, specific and weak unspecific, were predicted on
the channel walls and at the channel intersection. The
molecular diffusion of water in the silicalite found a barrier
for crossing between the straight and the zigzag channels. Next,
the analysis of the thermal motion predicted that at room
temperature, framework oxygen atoms incurring into the zeolite
channels significantly influence the dynamics of adsorbed
water.69
Further calculations were performed for ibuprofen (Ibu,
Scheme 2) release from pH-gated silica nanochannels.70 The
Ibu delivery process from cylindrical silica pores of 3 nm
diameter, with polyamine chains anchored at the pore outlets,
was investigated by means of massive molecular dynamics
simulations. High, low, and intermediate pH environments
were investigated. It was reported that the increment of the
acidity of the environment leads to a significant decrease of the
pore aperture, yielding an effective diameter, for the lowest pH
case, that is 3.5 times smaller than the one associated with the
highest pH one. The joint analysis of the corresponding Gibbs
free energy profiles for the Ibu delivery process, the time
evolution of its position within the channel, orientation of the
molecule, and instantaneous effective diameter of the gate
suggest a three-step mechanism for Ibu delivery. A comple-
mentary analysis of its translational mobility along the axial
direction of the channel revealed a subdiffusive dynamics in the
low and intermediate pH cases.70
2.2. Photoinduced Processes in Trapped Monomers and
Aggregates
In this section, results of theoretical predictions on the
interactions of dyes with the SBMs will be commented on.
First, we examine the effects of the interaction with the silica
environment on the absorption and emission spectra. Then, we
address its impact on the excited state lifetimes and finish with
the reports on interguests interaction that leads to energy
transfer (EnT) between nearby trapped dyes within SBMs pore
or cavity.
2.2.1. Impact of SBMs on Absorption and Emission
Spectra of Chromophores. When trapped fluorenone (FL,
Scheme 2) in the channels of zeolite L was theoretically
investigated, the interaction of its carbonyl group with the
potassium cations of the zeolite framework was found to be
responsible for its stabilization in the composites.71 The
calculations predicted optical anisotropy in this composite,
maintained upon contact with water, which can drastically alter
the preferred position of the dye in the silica nanostructure.
Such effects were calculated too for oxonine and pyronine
cationic dyes in zeolite L (Ox+ and Py+, respectively, Scheme
2).72 Different preferred dye molecule orientations were
obtained in the presence or absence of water, as a result of
stabilization of either the host or the guest. In the hydrated
composite, a perpendicular orientation of the Ox+ or Py+
molecules with respect to the zeolite channel axis was favored,
while the order of preferred orientations was reversed under
dry conditions.
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Similar conclusions were drawn from calculating the
preferred positions of FL in zeolite L.73 As commented upon
above, the overall redshift of features in the absorption
spectrum in hydrated zeolite L from their positions in
cyclohexane samples was found to originate mainly from the
interactions between the counterions of the zeolite and the
carbonyl group of FL. It was found that the direct effect of
water molecules on the excitation energies of the dye is
negligible, but they do affect its orientation inside the zeolite
channel. The role of water molecules in Ibu interactions with an
amorphous silica surface was also studied.74 Simulations
revealed that the silica surface exhibits a higher affinity for
water than for Ibu. Van der Waals forces are the leading
contributor to its adsorption, independently of whether the
drug is H-bonded directly to the surface or via water molecules.
The effect of immobilization of cationic Ir(III) complexes on
sodium aluminosilicate mesoporous glass was experimentally
and theoretically studied.75 The calculations considered the
chemical environment of the Ir (III) complex by including both
the counterion (representing the active site of the matrix) and
the dielectric constant of the matrix. At low dielectric constants
(ε < 20), the counterion has a strong influence on the energy
and orbitals of the excited states. The influence of zeolite Y
framework on a nickel(II) complex was also examined.76 The
deviations that occur in the geometry of the complex upon
encapsulation result in changes of the highest occupied
molecular orbital and lowest unoccupied ones (HOMO and
LUMO respectively) energy levels, and in the electronic
properties of the system. The calculated chemical hardness
confirmed that the encapsulated nickel(II) complex is more
stable than the free one, and it can undergo more easily
electron transfer (ET) reactions, thus performing photo-
catalysis better than the free one.
The calculations of absorption spectra of organic molecules
interacting with SBMs were performed for possible applications
in catalysis. For example, (poly)aromatic cationic compounds
have characteristic absorption bands in the visible region, and
the benefits of using a theoretical approach to identify them as
potential candidates was suggested.77 The origin of their
absorption spectra has been attributed to structurally different
species on the basis of calculated excitation energies. Moreover,
it was shown that the use of time-dependent density functional
theory (TD-DFT) computations on gas-phase compounds was
insufficiently accurate.78 It was suggested that molecular
dynamic simulations are necessary to consider geometrical
deformations of carbonaceous compounds as these lead to
broad absorption bands: the results of such simulations were in
excellent agreement with the experimental data.
DFT/TD-DFT calculations were also used to explain the
result of experiments on t-azobenzene in Linde type L zeolites
(t-Ab and LTL in Scheme 2 and Scheme 1, respectively).79 In
contrast to its planar structure in solution, t-Ab is twisted in
LTL zeolites, as it is constrained by the framework. The
photophysical properties in acidic (H-LTL) and potassium (K-
LTL) forms of the zeolites were explained on the basis of
(n,π*) and (π,π*) transitions of the dye. In K-LTL zeolites,
both transitions are present in the absorption spectra, with
intensity maxima slightly red-shifted from their positions in
solution samples. In contrast, in H-LTL zeolite, the (n,π*)
transition was not observed as the lone electrons pair of the
nitrogen atom forms a H-bond with a Brønsted acid site in the
zeolite. These results confirmed that t-Ab was protonated in H-
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Chemical Reviews
Figure 5. (A) Molecular structure of DEAC molecule showing the dihedral angle, θ. (B) Ground and excited state potential energy and oscillator
strength as a function of θ. (C) Population density distributions as a function of time and θ. Reprinted with permission from ref 85. Copyright 2014
Elsevier B.V.
LTL, and that only this species can fluoresce, as it does not
connect with the dark (n,π*) state.
In addition to organic chromophores as guests, absorption
spectra of silica-encapsulated quantum dots (QDs) were also
investigated.80 Strong coupling between Cd2Te2 QDs and silica
shell was predicted, leading to the distortion of the silica
nanocage. Therefore, a direct electronic transition from the
occupied Cd2Te2 states to the outer silica nanocage excited
states (core-shell electronic transitions) was predicted. As a
result, the absorption peak of Cd2Te2 absorption spectrum is
shifted from 584 nm (isolated) to 534 nm when the QDs is
encapsulated by silica. In section 3.3, we comment on the
experimental observations and the involved EnT processes.
2.2.2. Impact on Excited-State Dynamics. Tetrame-
thylrhodamine isothiocyanate (TRITC, Scheme 2) in water and
covalently encapsulated to silica nanoparticle was studied by a
combination of TD-DFT and classical molecular mechanic
simulations, in addition to fluorescence spectroscopy.81 The
authors studied the changes in the molecular structure upon
electronic excitation and found that the variations were indeed
smaller for the encapsulated dye than in water. A subsequent
report explained the reason for the long excited state lifetime of
TRITC in silica nanoparticles.82 It was found that the crossing
from (π,π*) to (n,π*) state in water solutions is reduced by the
rigid environment of the silica shell, decreasing the fluorescence
quenching of the bright (π,π*) state by the dark (n,π*) one.
Two 7-aminocoumarin dyes that were incorporated into
MCM41 were studied using DFT and TD-DFT calculations
(coumarin 339 and 340, C339 and C340, respectively, Scheme
2).83 It was shown that the interaction of the carbonyl groups of
these dyes with the silanol groups on the silica surface is
responsible for stabilizing them in the composites and is
strengthened upon photoexcitation. As a result, the computed
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absorption and emission spectra of the incorporated dyes were
red-shifted compared to the spectra in toluene. C339 and C340
molecules were further studied theoretically by comparing their
photobehavior in ethanol and in Pluronic silica nanoparticles.84
Two molecules from that family were investigated: one of them
with flexible alkyl moieties and the other one has rigid alkyl
groups. Electronic excitation results in a twisted-intramolecular
charge-transfer (TICT) state in the former molecule, which
leads to a short fluorescence decay in solutions that is different
from that of the rigid molecule. However, both molecules
showed similar photophysical behaviors when embedded into
the nanoparticles, which was shown to be governed by the
drastically hampered deactivation of the flexible molecule in the
silica matrix.84 Redshift in emission spectra (dye in MCM41 vs
toluene solution) and their temperature effects were calculated
in a subsequent work by the same group.85 The authors used
TD-DFT with a generalized Smoluchowski equation approach
to compute time-resolved spectra of 7-diethylaminocoumarin-
3-carboxylic acid butylamine ester dye free in ethanol and
encapsulated in silica nanoparticles (DEAC, Scheme 2 and
Figure 5A). The predicted emission quenching occurred
because of the conformational change from an ICT state to a
TICT state (Figure 5). The rotation that leads to this change
was significantly hindered when the dye interacted with silica.
The theoretically predicted restrictions in rotational motions of
encapsulated molecules found confirmation in experimental
reports (see section 3).
Possible ET reactions from the excited states of carotenoids
to the mesoporous frameworks of MCM41 and its derivatives
were studied, being of possible applications in dye-sensitized
solar cells. Sections 3 and 5 comment on the involved events
and their applications in photovoltaics. It was found that the
formation of H-bonds stabilizes the canthaxanthin (CAN,
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Chemical Reviews Review

Figure 6. (A) Kohn−Sham molecular orbitals of the dimer of 7-aminocoumarin. Reprinted with permission from ref 84. Copyright 2013 Royal
Society of Chemistry. (B) Illustration of the distribution of guest (green bars) in a homogeneous (right) and inhomogeneous way (left) inside a
zeolite L crystal for high loadings. Their impact on FRET dynamics is highlighted by the different number of transfer steps (red circles) expected in a
trajectory (indicated as black lines). The blue lines show the distribution of guests along the channels. Reprinted from ref 93. Copyright 2016
American Chemical Society.

Scheme 2) molecule in CuMCM41 and affects its charge
distribution and LUMO energy.86 As a result, CAN exhibits a
lower photoinduced ET efficiency than β-carotene, for which
no H-bond between the dye and the host is formed. This effect
was further studied in a subsequent work by the same group,
predicting two types of H-bonds between the OH group of
retinol and silanol ones on the surface of MCM41.87 One of
these H-bonds decreases the LUMO energy of the interacting
carotenoid and stabilizes its neutral species more than its radical
cation, thus disfavoring photoinduced ET from the carotenoid
to MCM41. The opposite behavior was found for the second
type of H-bonds.
2.2.3. Impact of Guest Aggregation. Increasing the
concentration of a guest in the silica framework usually leads to
aggregates formation. Formation of these entities is closely
related to the occurrence of EnT between nearby adsorbed
guest molecules. EnT from photoexcited guest (donors) to
acceptor molecules behaves according to the model of Förster
resonance EnT (FRET).88 In particular, the fluorescence
kinetics for such a process should be described by a
stretched-exponential function (sometimes also called Kohl-
rausch decay function).88,89 The equation has the following
formula: f (t) = A exp [(−t/τs)α], where τs is a characteristic
time of the decay and α is the heterogeneity parameter (α = 1
for monoexponential decay, and a smaller value indicates more
dispersive kinetics and large sample heterogeneity).88,90−92 For
the 7-aminocoumarin interacting with SBMs discussed
previously, the effect of the dye concentration in a matrix on
the fluorescence quenching was also theoretically explored.84
The calculations indicated that the strong quenching is
attributable to the formation of excimers with a CT character
upon excitation of the monomeric species. The LUMO of the
calculated aggregate (dimer) has a strong bonding character
(Figure 6A). The excitation of an electron from the HOMO of
K DOI: 10.1021/acs.chemrev.7b00422
a monomer to the binding LUMO of the dimer leads to a
strong interaction between the two molecules. Interestingly, the
results address two commonly observed dynamic properties of
nanoconfined chromophores that have opposite effects. On one
hand, blocking the twisting of a molecule encapsulated in SBMs
can lead to a longer excited state lifetime. On the other hand,
the interaction of guests with the silica surface may induce the
formation of their aggregates, which accelerates the deactivation
of the excited state due to the EnT between the bright and the
dark states in the aggregates.
The orientation and photophysical properties of methyl-
acridine dye in zeolite L were calculated (MeAcr+, Scheme 2).94
The most stable orientation of this guest results in both its long
and short molecular axes being nearly perpendicular to the
channel axis and was found mainly determined by dye-zeolite L
electrostatic interactions in addition to that with the cosolvent,
water. The optimized conformations were used to explain the
observed EnT processes (self-absorption). FRET in dye-filled
monolithic crystals of zeolite L was recently modeled using
Monte Carlo and molecular dynamic simulations.93 Under ideal
conditions (homogeneous dye distribution), very high exciton
diffusion rates were expected in zeolite L. However, the
inhomogeneity of the dye distribution along with the 1D
channels led to a large change in the exciton dynamics that
reduces the exciton lifetimes and modifies the dimensionality of
the energy transport (Figure 6B).
FRET was also studied in LTL zeolites and interpreted with
the help of theoretical calculations.95 Cyanine (1,1′-diethyl-2,2′-
cyanine iodide, PIC) and acriflavine hydrochloride (AF) dyes
acted as energy donor and acceptor partners, respectively
(Scheme 2). Energy was transferred from excited PIC to AF
that were adsorbed into the internal surfaces of zeolite LTL. A
redshift of AF emission band in the protonated LTL zeolite was
explained in terms of a conversion from a cationic to a
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Chemical Reviews
Scheme 3. Molecular Structures of the Compounds Interacting with SBMs and Discussed in the Proton-Transfer Section 3.1
protonated AF form. The experimental reports on EnT in
SBMs, and its application are highlighted, respectively, in
section 3.3, and section 5.
In this part, we have commented on how theoretical studies
have become gradually important tools in explaining and
predicting the short-time dynamics in SBMs. A large part of
theoretical research is devoted to modeling solvation dynamics
in silica-based hosts and the resulting effects of different local
environment at different positions in the silica pores. Other
studies predicted how the interaction of the chromophore with
the host changes its photophysical properties and how it affects
the stationary absorption/emission spectra and the photo-
dynamics upon light excitation.
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3. ENSEMBLE AVERAGE TIME-RESOLVED STUDIES OF
PHOTOINDUCED PROCESSES IN SILICA-BASED
MATERIALS
3.1. Proton-Transfer Reactions
Proton-transfer (PT) reactions are intensively investigated
since they play important roles in a wide variety of chemical
and biological processes, such as acid−base reactions,
biochemistry, and catalysis (see Scheme 3 for molecules
involved in PT reactions discussed here).32,37−39,96−107 More-
over, the study of these reactions has resulted in the
development of many applications, such as fluorescent
chemosensors,108,109 laser dyes,110−114 ultraviolet (UV) photo-
stabilizers,115 photoswitches,116−119 and organic optoelectronic
materials.120−122
These reactions occur between proton (or hydrogen atom)
donor (typically −OH, −NH2, and −SH) and acceptor (CO,
−N, base and some solvents) groups. The reaction can be
inter- or intramolecular and can be activated thermally or by
light; the process can occur through or without a
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Chemical Reviews
barrier.32,97,101,105,107 Aromatic molecules that contain an acidic
proton in their structures can undergo intermolecular PT
reactions in both the ground (ground-state proton transfer,
GSPT) and the electronically excited (excited-state proton
transfer, ESPT) states.37,98,101,123,124 Upon electronic excitation,
these molecules become strong acids (photoacids) that can
undergo an ESPT reaction with a neighboring base molecule,
such as water, alcohols, or amines.39,102,123−127 Since Weller’s
and Eigen’s works,96,128−130 the mechanisms of PT reactions
have been intensively investigated from experimental and
theoretical points of view.100,101,107,124,127,131−133 The Smolu-
chowski-Collins-Kimball (SCK) model has been used to
describe this type of reactions.134−137 This model shows how
the diffusion of the acid and the base through the solvent plays
an important role in the mechanism, as the reactants should
approach each other at a specific distance for the PT reaction to
occur. The surrounding environment may play a key factor in
solute/solvent interactions and subsequent reorganization.
Therefore, the global dynamics of these reactions are
determined by diffusion, interactions with the solvent, and
the adiabatic and nonadiabatic nature of the potential energy
surfaces (PES), as well as by the type of the prototropic
groups.123,124,138−141
In bifunctional organic molecules that contain both the
proton donor and acceptor groups in close proximity, an
intramolecular PT reaction in the ground (GSIPT) or
electronically excited (ESIPT) state can occur.32,99,117,142
Because of the chemical structure and the positions of the
partners in these bifunctional systems, an intramolecular H-
bond (IHB) is formed in the ground state (S0), usually
producing a species called an enol (E) form. Consequently,
upon electronic excitation of E, an intramolecular electronic
charge redistribution occurs in E* that leads to the formation of
the keto (K*) or zwitterion (Z*) tautomer. When these species
return to S0, they can be stabilized in this or other tautomeric
forms (e.g., rotated K), or return to the E species.143−148 The
mechanism and rate constant of the ESIPT reactions depend
on the PESs of the E* and K* tautomers in the first
electronically first excited single state (S1).101,149 The presence
or absence of barriers for both processes in S0 and S1 opens the
possibility of controlling the related spectroscopy and
dynamics.44,150−155 Thus, for a PES without an energy barrier
between the wells of E* and K* species, the ESIPT reaction is
ultrafast (fs regime) and irreversible.101,156 When the PES has a
barrier in the conversion of E* to K*, the reaction may be
reversible or irreversible but will be slower (ps−ns regime) than
in the barrierless situation.34,157−164 An accurate description of
the reaction dynamics at the PESs of ESIPT processes in gas
phase requires at least two reaction coordinates: (i) the proton
motion within the corresponding IHB and (ii) the vibrational
or torsional (angle) mode involving the distance between the
partners; the angle between the involved moieties in the
transfer could be important in the global reaction dynamics and
subsequent processes.97,99,101,107 In the presence of an energy
barrier in the PESs, the proton motion may occur via tunneling,
which adds another (quantum) dimension to the reaction. In
solution, the PESs might be complex, involving a solvent
coordinate where its polarity and H-bonding could play an
important role in shaping the spectroscopy and dynamics. The
earliest studies of proton-transfer dyes mainly used fluorescence
spectroscopy because the photoproduced K* (or Z*) generally
emits with a large Stokes shift (6000−10000 cm−1). Advances
in laser spectroscopy gave details on PES’s reactions at the
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f em t o s e c o n d t i m e s c a le i n g a s a n d c o n d e n se d
phases.29,32,40,100,106,149,157,165−170 Coupled proton and electron
motions in the molecular system, of great importance in many
chemical and biological systems, have been experimentally and
theoretically examined.34,171−173 The experimental and the-
oretical findings not only generate new knowledge but also
open new research fields with possible applications in sensing,
catalysis, drug delivery, photovoltaics, and photonics (section
5).
Both inter- and intramolecular PT dynamics are sensitive to a
variety of environmental properties, such as polarity, hydro-
phobicity, viscosity, acidity, basicity, and H-bonding abil-
ity.117,120 This sensitivity to the surrounding characteristics
makes PT systems potential candidates as environmental
sensors, an important aspect that has been explored by several
groups.32,38,117,120 Researchers took advantage of this virtue by
using molecules that transfer protons to characterize the nano-
and microenvironments in cavities and pores of SBMs. In these
systems, the specific and nonspecific molecular interactions
between the trapped guest (the proton-transfer dye) and the
host, as well as with the caged solvent molecules, can be
modified to tune the spectroscopy and dynamics of the formed
composites (dye/SBMs).
3.1.1. Intermolecular Proton-Transfer Processes. In the
presence of bases (solvent or another solute), many molecules
that have acidic protons undergo intermolecular PT processes
in both S0 and S1 states (GSPT and ESPT, respec-
tively).98,123,124,174−178 Central to this review, most of the
SBMs have OH groups, and thus are interesting material
models to study the PT reaction dynamics of guest molecules
within their pores or channels.
3.1.1.1. Molecules Exhibiting Deprotonation with the
Framework in S0 and S1 States. Upon encapsulation of
chromophores in SBMs, they can establish an intermolecular
H-bond with the surrounding framework; protonation or
deprotonation in the ground and/or excited state are possible
events. 2-Naphthol (2-NpOH, Scheme 3) is a classic example
that demonstrates a PT reaction with a H-bonded acceptor
group (water, alcohols, amines, etc.). 2-NpOH emission in
water solutions is dominated by its anion’s (2-naphtholate)
emission as a result of a large change in the acidity of 2-NpOH
in S1 (pKa = 9.5 and pKa* = 2.8).124,179−182 Its spectroscopy
and related dynamics are pH-dependent.183 In acidic and
neutral media (pH = 1−7), which have relatively high [H+], the
ESPT reaction is described by a reversible mechanism (Figure
7). In this accepted scheme, kPT and krec are the deprotonation
and recombination rate constants, while kD and k−D are the
forward and reverse diffusion-controlled rate constants that can
be obtained from the Debye-Smoluchowski equation.124,183,184
In contrast, in alkaline conditions (pH > 7) and in the presence
of sodium acetate, the ESPT reaction moves forward and is
Figure 7. General scheme of a reversible excited-state intermolecular
proton transfer (ESPT) process in excited HPTS. Reprinted with
permission from ref 186. Copyright 2016 Royal Society of Chemistry.
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Chemical Reviews Review

Figure 8. (A) Normalized (to the maximum intensity) fluorescence spectra of HPTS (solid line), HPTS/MCM41 (dashed line), and HPTS/
MCM41 upon addition of 20 μL of water (dotted line) in dichloromethane suspensions. Schematic illustration (not in scale) of (B) HPTS/MCM41
in a dichloromethane suspension, and (C) HPTS trapped within a water drop adsorbed on the MCM41 surface. The insets of (B) and (C) show the
wavelengths corresponding to the emission intensity maxima and the fluorescence lifetimes (τ, τRO) of the formed species and of the values of proton
transfer (kPT) and recombination (krec) rate constants. Adapted with permission from ref 186. Copyright 2016 Royal Society of Chemistry.

Figure 9. Emission decays of HPTS/MCM41 in dichloromethane suspension containing (A) water and (B) deuterium oxide. Reprinted with
permission from ref 186. Copyright 2016 Royal Society of Chemistry.

irreversible.183 In neutral conditions, the proton motion occurs
with a kPT = 7.6 × 107 s−1 and krec = 4.7 × 1010 M−1 s−1,
generating an anion that has a fluorescence lifetime of 9
ns.183,184 When 2-NpOH is caged in β-cyclodextrins (β-CDs),
the ESPT reaction exhibits a reversible mechanism with kPT =
2.2 × 107 s−1 and krec = 2.3 × 1010 M−1 s−1, which are slower
than those recorded in bulk water.182,185 The observed
reduction of kPT and krec values is due to the encapsulating β-
CDs cage having a less polar and less protic character than the
bulk water microenvironment does, reflecting the important
role that the host plays in the PT dynamics.44,46,182 In contrast,
the fluorescence lifetime of the caged anion (τAN = 10.5 ns) is
longer than that in aqueous solutions due to the protection
provided by the CD cavity. 44,182 When 2-NpOH is
encapsulated in solid NaX zeolites, a faster ESPT reaction
(kPT = 3.3 × 109 s−1) and a slower recombination process (krec
= 8.3 × 108 M−1 s−1) were reported.179 The larger value of kPT
observed for these hybrid complexes, in comparison with that
in water solutions (kPT = 7.6 × 107 s−1), is explained in terms of
a stronger basic character of the NaX host. The formation of
strong H-bonds between the silicate framework (Si−O−Si) and
trapped 2-NpOH molecules leads to a fast deprotonation of the
latter.179 When the trapped anion interacts with the NaX
material, it lives 4.7 ns, which is significantly shorter than in
water solutions (9 ns), reflecting an enhanced intersystem
crossing in the zeolite nanocavities.179
Another well-known photoacid molecule, 8-hydroxypyrene-
1,3,6-trisulfonate (pyranine, HPTS, Scheme 3), was inves-
tigated in the presence of mesoporous MCM41 materials.186
N DOI: 10.1021/acs.chemrev.7b00422
When HPTS in water solutions is excited, its acidity
significantly changes (pKa = 7.7 to pKa* = 0.6).187 In neutral
water solutions, HPTS undergoes a reversible ESPT reaction
that is characterized by kPT and krec of 1 × 1010 s−1 and 6 × 109
Å s−1, respectively.186,188 To understand the dynamics of the
interaction of HPTS with SBMs, we briefly discuss its behavior
in other hosts such as CDs and the human serum albumin
(HSA) protein. The ESPT reaction of HPTS within these hosts
follows an irreversible mechanism with a rate constant (kPT)
that is lower than that in bulk water.189−191 The change is
attributed to the slow solvation dynamics of the encapsulated
water inside or at the pore gates of these hosts (biological
water).189−191 Within these hosts, HPTS exhibits two different
PT pathways that are characterized by times of 150 fs and 1.2
ns in HSA, and 140 ps and 1.4 ns in γ-CD, reflecting the
heterogeneity of the formed complexes.190,191 By heterogeneity,
we mean that the trapped dye molecules are found in locally
different environments and positions within the chemical (CD)
and biological (HSA protein) pockets. For the HPTS:HSA
complexes, the shortest time is due to a strong interaction of
the dye with the host in which a direct reaction with the
carboxylate groups of the protein’s amino acids is suggested.
The slower process is assigned to a PT reaction with the
biological encapsulated water molecules, which have slower
dynamics.190,191 These results once again show the importance
of the host’s nature on the photobehavior of trapped H-bonded
aromatic molecules.
However, HPTS does not undergo PT when it interacts with
the surface of MCM41 materials in dichloromethane
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Chemical Reviews
suspensions, and thus, the emissions of the protonated
monomer and adsorbed aggregates were recorded (Figure
8).186 The emission spectrum is centered at 430 nm, and the
fluorescence lifetimes of these species are 350 ps and 2.5 ns,
respectively. Adding water (1%) to these dichloromethane
suspensions leads to a reversible ESPT reaction and a strong
emission of the anion.186 In this case, the PT dynamics are
slower than those observed in bulk water, with PT and
recombination rate constants kPT = 5.4 × 109 s−1 and krec = 2.2
× 109 Å s−1, respectively.186 The decrease in the values of the
rate constants is explained in terms of a decrease in the HPTS
photoacidity due to a partial loss of the negative electronic
charge of its SO3− groups that are H-bonded to the
framework.186 Furthermore, the immobility of the HPTS
anions on the silica frameworks leads to a slower recombination
process.186 When normal water is replaced by deuterated one,
the PT and recombination processes of these complexes are
even slower, with kPT = 2.7 × 109 s−1 and krec = 1.7 × 109 Å s−1
(Figure 9). The study reported that the kinetic isotope effects
(KIEs) are 2 for (kHPT/kDPT) and 1.3 for (kHrec/kDrec), being
larger for the PT process than the normal one in bulk water
(1.4).186 Thus, the H-bonding interactions between HPTS and
the MCM41 framework and the restricted diffusion space
available to the adsorbed HPTS result in slower dynamics.186
However, a different behavior was observed when HPTS
interacts with other SBMs such as alumino-silica surfaces and
hydrated porous silicon (10 nm pore size).188,192 For both
complexes, the ESPT mechanism is similar to that observed for
HPTS in bulk water. This similarity is because the HPTS
molecules are covalently linked to the alumino-silica surfaces
and retain their photoacid character, while in the hydrated
porous silicon, the large pore size of the host does not affect the
ESPT dynamics.188,192 Clearly, the different behaviors of HPTS
when interacting with these materials reflect how the molecular
environment and the restriction of the host affect the ESPT
reaction of the PT dye and its related dynamics.
The hydroxyquinoline family, having amphoteric character,
has been intensively studied due to the possibility of assisted
ESPT reactions with protic media (water, alcohols, acetic acid,
or ammonia, among others).138,139,193−198 As a result,
hydroxyquinolines were selected as good candidates to study
the catalytic properties of SBMs as single and double PT
reactions can occur in the pores of these materials.143,144,199−201
In a neutral aqueous solution, 6-hydroxyquinoline (6-HQ,
Scheme 3) exhibits an ESPT reaction in a stepwise fashion: an
initial proton release from the OH group of 6-HQ that
produces the anion (AN) in ∼20 ps (E*→ AN*) followed by a
PT to the nitrogen atom of AN* that forms the final tautomer
(AN*→ T*) in ∼45 ps (Figure 10).202,203
When caged in β-CD, 6-HQ shows a similar mechanism.202
The forward reactions (k1 and k2), with time constants of ∼380
ps and ∼360 ps, are 19 and 8.4 times slower than those in
water, respectively.202 However, the reverse PT events (k−1 and
k−2) are slightly accelerated by CD’s encapsulation.202 When
trapped in NaX and NaY zeolites, 6-HQ exhibits a similar
reversible ESPT process.199 The UV absorption spectra show
three bands centered at 325, 365, and 430 nm, indicating three
possible prototropic species (E, AN, and Z, respectively) in the
S0 state. In contrast, the emission spectra only exhibit two
bands, which have intensity maxima at 400 and 510 nm,
assigned to the emission of AN* and Z*, respectively. No
emission signal was detected from E*, suggesting that almost all
the molecules in this form readily deprotonate. The relative
O DOI: 10.1021/acs.chemrev.7b00422
Review
Figure 10. Proposed diagram of proton transfer and relaxation of the
prototropic species of excited-state 6-HQ in microporous catalytic
faujasite zeolites. Adapted with permission from ref 199. Copyright
2010 Wiley-VCH.
intensities of AN* and Z* bands depend on the properties of
the zeolite’s cage: AN* emission is predominant in NaX, while
that of Z* in NaY.199 The authors explained this difference in
terms of the zeolite basicity. Since NaX is more basic than NaY,
the AN* population is larger in its cages. The ESPT times and
the values of the fluorescence lifetimes of the different formed
species of 6-HQ in these zeolites (kN−1, kAN−1, and kT−1 for the
neutral, anion, and zwitterion forms, respectively) are shown in
Table 1.199
Clearly, the zeolite confinement decelerates the forward
reactions (from 20 to 70 ps for k1−1 and 43 to 400 ps for k2−1)
and accelerates the backward ones (from 380 to 140 ps for
k−1−1 and 1 ns to 750 ps for k−2−1),199 when compared with the
rate constants in water solutions.202,203 These photophysical
changes reflect that the zeolite confines the contact ion pairs to
be closer than they are in bulk water, thus enhancing the
forward reactions.199 Note that within CDs, the forward
reactions (380 and 360 ps) are even slower than in the zeolite
complexes.202 Confined water in the CD cavities leads to slower
molecular dynamics.44 However, within zeolite cavities, where
there is no confined solvent (or its population is very weak),
the dynamics are only affected by the specific and nonspecific
interactions with the acidic and basic sites of the framework.
These examples nicely show the relevance of the medium
(solution, suspension, or solid) in exploring the photodynamics
of these confined systems. On the other hand, the kinetic
constants of the PT and recombination processes of 6-HQ
within NaX and NaY zeolites are also affected by the acid/base
properties of these hosts (Table 1).199 The enol deprotonation
process (k1−1) is slightly faster in NaX, a zeolite with a high
basicity, than in NaY (67 vs 71 ps, respectively), while the
reprotonation (k−1−1) is slower (180 vs 120 ps, respectively).
Similarly, the anion protonation (k2−1) is slower in NaX than in
NaY, and its redeprotonation (k−2−1) is faster.199 In NaX
complexes, the predominant species is the anion as it is
reflected by its large contribution (at ∼400 nm) to the time-
resolved fluorescence spectra (Figure 11).199 Thus, the host
properties play an important role in determining the pathway
and the rate constants of the ESPT reactions: the OH-group
deprotonation processes are the most favored in a basic host
(NaX), while the imine protonation processes are favored in
more acidic ones (NaY).199 These results are in agreement with
the fact that the protonation of the 6-HQ anion is largely
favored in the presence of acetic acid.195
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Chemical Reviews
Table 1. Kinetic Constants of Excited-State Tautomerization and Relaxation of 6-HQ Encapsulated in Zeolitesa
zeolite k1−1 (ps) k−1−1 (ps) k2−1 (ps)
NaX 67 180 420
NaY 71 120 380
a
Reprinted with permission from ref 199. Copyright 2010 Wiley-VCH.
Figure 11. Time-resolved fluorescence spectra of 6-HQ trapped in (A)
NaX and (B) NaY after a time delay of 0 (purple), 70 (blue), 200
(green), 500 (yellow), and 2000 ps (red). The inset in (A) is a cartoon
(not to scale) of 6-HQ encapsulated in a faujasite zeolite nanocavity.
Reprinted with permission from ref 199. Copyright 2010 Wiley-VCH.
7-Hydroxyquinoline (7-HQ, Scheme 3), a well-studied
quinolone derivative, also exhibits single and stepwise double
PT reactions.143,144,200 In water solutions, the OH-deprotona-
tion and imine protonation processes occur in both S0 and S1
states and are reversible in the former.204 Upon electronic
excitation of 7-HQ (to S1), the time constants of these acid and
base processes are 40 and 160 ps, respectively.204 Several
groups have reported that the photobehavior of 7-HQ
prototropic forms is sensitive to the confining environ-
ment.125,139,185,187,204,205 For example, when 7-HQ is caged in
β-CD, its OH-deprotonation is slower (170 ps), while its imine
protonation is faster (85 ps) than those observed in water
solutions.39,204 Moreover, in these cavities, the enol population
is the predominant form, while in pure water, the zwitterions
dominate. This difference reflects the hydrophobic nature of
the CD interior stabilizing the enol form and the slowing down
of the double PT processes that occur at the two gates of CD
cage.185 Similar behavior was observed in nonaqueous protic
solvents, such as alcohols: an H-bond bridge is formed with the
enol to function together as a proton relay.139 Solvent
reorganization to reach an appropriate 7-HQ/solvent config-
uration is an important factor to consider in PT reac-
tions.139,184,206,207
When 7-HQ is within regular MCM41 materials in
dichloromethane suspensions, its OH-deprotonation and
imine protonation are irreversible.144,179 Contrary to the
dynamics in bulk water, both the AN and Z/K forms are
stabilized in S0 when the dye is caged in MCM41 pores,
showing how the hydrophilicity, structure, and confinement of
this host affect the formation and stability of these
species.143,144 Moreover, the presence of Al atoms in
MCM41 (AlMCM41) highly stabilizes the AN form in S0.143
The incorporation (doping) of Al atoms into the silica
framework introduces negatively charged sites that are able to
P DOI: 10.1021/acs.chemrev.7b00422
Review
k−2−1 (ps) kN−1 (ps) kAN−1 (ps) kT−1 (ps)
710 1100 9600 15600
770 1450 12200 18000
interact with the labile protons of the E form of 7-HQ,
stabilizing the trapped AN.143 The emission spectra of these
composites are rather complex, displaying signals from 325 to
650 nm. On the basis of the excitation-dependent emission
spectra and the lifetime distributions, the authors assigned the
emission to E*, AN*, and Z* that are all caged and H-bonded
to the framework. Their fluorescence lifetimes are 0.26, 1.5, and
5.5 ns, respectively.144 Femtosecond emission studies of caged
E* revealed the deprotonation and protonation dynamics
within the MCM41 and AlMCM41 composites (Figure
12).143,144 The obtained time constants are 0.3 and 3 ps,
Figure 12. Femtosecond (fs)-emission transients of 7-HQ interacting
with MCM41 in a dichloromethane suspension. Reprinted from ref
144. Copyright 2010 American Chemical Society.
respectively, in MCM41, while in AlMCM41, both processes
are slower (0.5 and 6 ps, respectively), showing the importance
of specific and nonspecific interactions with the nanohosts in
this guest’s dynamics and spectroscopy.143 Both processes are
significantly faster than those in water (40 and 160 ps) and CD
(170 and 85 ps) solutions, which emphasizes direct PT events
in robust composites, where confinement, specific, and
nonspecific interactions play a major role in its photobehavior.
Because of these interactions with the host, even molecules
that exhibit ultrafast ESIPT reactions in solutions can undergo
ESPT processes when they are encapsulated in micro- or
mesoporous materials, making very rich their spectroscopy.
This possibility is illustrated by the cases of 2-(2′-
hydroxyphenyl)benzothiazole (HBT), 2-(2′-hydroxyphenyl)-
benzoxazole (HBO), and other derivatives when they interact
with zeolites and mesoporous materials (Scheme 3).208−214 In
solutions and upon electronic excitation, this kind of molecules
exhibits ultrafast ESIPT reactions (<50 fs) to produce K*
tautomers, which exhibit an emission with a large Stokes
shift.145,146,167,215−219 Several studies have demonstrated that
the ESIPT mechanism is also affected by solvent properties: in
polar and protic media, intramolecular and intermolecular H-
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

Figure 13. (A) Schematic representation of HBO structures in S0 in dichloromethane solution (Esyn and Eanti) and interacting with NaX/NaY
zeolites [Esyn bonded to the surface (E′) and anion populations within the supercages (AN1) and within the microchannels (AN2)]. (B)
Femtosecond-emission transients of HBO interacting with NaY and NaX in dichloromethane suspensions. Reprinted from ref 213. Copyright 2014
American Chemical Society.

Figure 14. Steady-state emission spectra of (A) HBTNH2−SiO2, (B) HBTNH2-MCM41, and (C) HBTNH2−AlMCM41 in acetonitrile
suspensions. The insets show the composites structure. Adapted from ref 209. Copyright 2010 American Chemical Society.

bonding interactions compete.215,216,220−225 Therefore, one can
expect that the encapsulation of these molecules in SBMs,
which are polar and hydrophilic in their regular structures, may
generate rich spectroscopy and dynamics of different confined
PT reactions. This richness was observed in HBT.107,111 In
alkaline water and methanol solutions, this molecule undergoes
ESPT in 1.6 ps and becomes an anion in 4.4 ps.212 When HBT
is encapsulated in faujasites (FAUs) and mordenite framework
inverted (MFI) zeolites, the ESPT reaction occurs in 1.5
ps.208,212 This result demonstrates that the deprotonation
processes in water solutions and in FAU zeolites are not very
different, suggesting that in the composites, the encapsulation
generates a PES that is not very different from that in water.212
When HBO, a molecule structurally comparable to HBT, is
confined within FAU zeolites, a similar photobehavior was
observed.213 In alkaline methanol and ethylene glycol solutions,
it exhibits an ultrafast ESPT reaction (<100 fs) that is followed
by ICT (1.2 ps) and a twisting motion (12 and 20 ps in
methanol and ethylene glycol, respectively).213 When it is
encapsulated in NaX and NaY zeolites in dichloromethane
suspensions, it exhibits a similar ultrafast ESPT reaction (<100
fs), but the subsequent ICT process is slower (2.5 ps) and the
twisting motion is now canceled (Figure 13).213 In the NaX
and NaY complexes, two anion populations, with fluorescence
lifetimes of 800 ps (AN1 encapsulated within supercages of
Q DOI: 10.1021/acs.chemrev.7b00422
∼13 Å in diameter) and 2.5 ns (AN2 trapped in nanochannels
of ∼8 Å in diameter that connect the supercages), are observed.
The greater restriction of motion within the nanochannels, due
to the smaller pore diameter, precludes the possibility of a
conformational change (twisting) in the confined anions and
thus increases its emission lifetimes. The presence of different
anion populations, compared with the single anion observed in
alkaline methanol and ethylene glycol solutions (τAN = 3 ns),
reflects the heterogeneous distribution of HBO molecules
resulting from different specific and nonspecific interactions
with the framework.213
An HBT derivative, 2-[5′-N-(3-triethoxysilyl)propylurea-2′-
hydroxyphenyl]-benzothiazole (HBTNH2, Scheme 3), was
covalently bonded to the surfaces of silica nanoparticles and
mesoporous materials (Figure 14).209 In these complexes, an
ESPT reaction took place between the dye and the silica
framework.209 Steady-state experiments showed that in the
amorphous silica nanoparticles, anions formation occurs,
although stronger emission is observed from the K* structure
(Figure 14A).209
However, when HBTNH2 is bonded to the MCM41 and
AlMCM41 frameworks, the interactions with these hosts lead
to a greater yield of anions and an increase in its emission
intensity (Figure 14, panels B and C).209 The replacement of Si
atoms by Al creates negative charges on the framework, which
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Chemical Reviews
Figure 15. Femtosecond emission transients of (A) HBTNH2, (B) HBTNH2−AlMCM41, (C) HBTNH2-MCM41, and (D) HBTNH2−SiO2 in
acetonitrile suspensions. Reprinted from ref 209. Copyright 2010 American Chemical Society.
increases its proton affinity and results in predominant anions
formation in the AlMCM41 materials.209 For the femtosecond
dynamics of these HBTNH 2 /SBMs complexes, the
AlMCM41’s composites also behave differently than
MCM41’s ones (Figure 15).209 The lack of the ultrafast
components in the fluorescence transients of the composites
with Al doping indicates that only the anion dynamics is
present. These transients have a 2.5 ps component, which is
assigned to vibrational relaxation (VR)/cooling processes, and a
2.5 ns lifetime assigned to the anions fluorescence (Figure
15B).209
The HBTNH2 case and the previously discussed example of
7-HQ nicely show that the replacement of few Si atoms by Al
ones modifies the structural, chemical, and physical character-
istics of the host framework (e.g., acid−base properties), which,
in turn, affects the guest’s photobehavior.143,209,226−228 Another
report on the encapsulation of 2-(4′-amino-2′-hydroxyphenyl)-
benzothiazole (AHBT, Scheme 3) by hybrid SBMs shows how
the substitution of OH groups by methyl (-Me) ones in the
silica framework modifies the photobehavior of the formed
composites.211 The amount of Me doping was changed from
1.4 to 9 mmol/g. Steady-state measurements showed that for
the OH materials, the AHBT open-enol form is stabilized in
both S0 and S1 states as a result of intermolecular H-bonding
with the host. However, for frameworks with Me-groups, the
formation of the K* tautomer is favored, and it is the main
caged species for the sample having the highest used methyl
content (9 mmol/g).211 The presence of Me-groups in the
silica-based framework increases its hydrophobic character and
thus decreases its capacity to H-bond with the dye. In this
manner, the closed E conformer of the dye, which results in the
K* species upon excitation, is stabilized. These results
demonstrate how the nature of the acid−base properties of
these SBM host, changed by either metal doping or
R DOI: 10.1021/acs.chemrev.7b00422
Review
methylation of their frameworks, affects the spectroscopy and
dynamics of the guest.
3.1.1.2. Molecules in S0 and S1 States that Exhibit
Protonation Processes with the Framework. Some molecules
can be protonated when they are encapsulated in SBMs.229−240
The guest forms one or more cationic species depending on the
available proton-acceptor groups and the acidity of the
encapsulating material.231−233 In these systems, intermolecular
H-bonds may stabilize the encapsulated guest and increase its
fluorescence lifetime.
Proflavine (3,6-diaminoacridine, PF, Scheme 3) is an
example of this kind of molecule.231−233 In aqueous solutions,
PF has a protolytic equilibrium involving mono- and dication
species.241 When it interacts with zeolites [Zeolite Socony
Mobil-5 (ZMS-5) and NaY] and MCM41 materials, different
photobehaviors were observed.231−233 Within the ZSM-5
zeolite, PF is present in the monocationic form (PFH+),
while within NaY and MCM41 materials, only its neutral form
is populated.231,232 The emission decays of these complexes are
biexponential, except the case of ZSM-5, whose decay fit
required a triexponential function.232 In the studied complexes,
two fluorescence lifetimes (∼2 and ∼5 ns) were assigned to PF
molecules that have weaker and stronger interactions with the
host, respectively.232 The ZSM-5 zeolite (MFI structure) is the
most acidic material among the zeolites used, and it is
characterized by a high content of protons in its
structure.4,242,243 Thus, the additional 1.3 ps component in
the emission decays of the PF/ZSM-5 complexes was assigned
to a protonation of PF from the framework.232 A comparable
behavior was observed in thionine (Th + , Scheme 3)
encapsulated in these materials.234 The fluorescence decay of
Th+ in an aqueous solution shows monoexponential behavior
with a time constant of 0.34 ns.244 However, when Th+ is
trapped in ZSM-5 and MCM41 materials, it exhibits a
biexponential decay with time constants of 0.33 and 1.77 ns
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
for ZSM-5 complexes and 0.16 and 0.31 ns for MCM41.234 The
similar 0.33 and 0.31 ns time constants are attributed to Th+
molecules that are adsorbed on the materials’ surface. In these
composites, Th+ molecules have little movement restriction and
strongly interact with the water molecules of the medium.234
The 1.77 and 0.16 ns times are assigned to encapsulated
monomer and dimer species, respectively. A femtosecond study
of Th+ in ZSM-5 revealed that the encapsulated monomer
species undergoes an interconversion between two protonated
forms in 2.6 ps. However, within MCM41, the protonation
process that was described above for the PF molecule does not
occur.234
Other molecules, such as ketones and benzophenone, have
been used as probes to characterize new solid sup-
ports.236−240,245−248 Benzophenone (BZP, Scheme 3) is widely
used to investigate the acidic character of the environ-
ment.247,248 As in the previous composites, BZP that is
encapsulated in materials that contain Brønsted or Lewis acid
sites [ZSM-5 and aluminophosphate (AlPO4) microporous
solid] exhibits protonation processes.238,239 In BZP/AlPO4
complexes, the luminescence spectra show two bands (440
and 470 nm) that are assigned to the H-bonded and protonated
BZP species, respectively. The behavior was compared with
that of BZP encapsulated in ZSM-5, a host that is less
hydrophilic and polar than AlPO4.238,239 When Na+ cations are
introduced into the ZSM-5 framework, Lewis acid sites are
favored. In sodium-doped ZSM-5 materials, in addition to the
H-bonded and protonated species (formed from the interaction
with the Brønsted acid sites of the host), the formation of
radical species was reported.238 The relative amounts of H-
bonded, protonated, and radical species depend on the number
and nature of the acidic sites in each material, making BZP a
sensor that provides relevant information about the acidic
characteristics of the host, which is of great importance in the
catalysis field.236−240
3.1.2. Intramolecular Proton-Transfer Reactions. As
said at the beginning of this section, the ESIPT reaction occurs
in organic bifunctional molecules that have both proton donor
and acceptor groups in close proximity.98,101 The dynamics of
the ESIPT reaction may depend on the environmental
properties such as its polarity, viscosity, and ability to form
H-bonds in the same manner as the ESPT reac-
tion.117,120,161,215,216,220,221,249−254
Understanding the ESIPT reaction and the possible
subsequent processes such as rotation or isomerization is
paramount to deciphering fundamental atomic motions but
also for designing new materials for photoswitches, sensors,
energy storage and nanomedicine devices, to cite a few
applications.43,255−258 For example, the encapsulation of
photochromic aromatic molecules, which undergo ESIPT and
subsequent isomerization, is of great interest to the
fundamental knowledge and applications.259−273 Sudan I (1-
phenylazo-2-naphthol, Scheme 3), which belongs to the group
of diazo-conjugate dyes, has been studied in FAUs (NaX, LiX,
MgX, and NaY) and MCM41 in several solvent suspen-
sions.260,261 In solution, it exhibits an ESIPT reaction (<50 fs)
that in S1, produces a trans-ketohydrazone (trans-HYZ)
structure, which subsequently isomerizes (by rotation, inver-
sion, or some mixed mechanism) in an ultrafast fashion to a cis-
ketohydrazone (cis-HYZ) structure that has a fluorescence
lifetime shorter than 2 ps (Scheme 3).259 The shorter lifetime
of cis-HYZ is due to a twisting motion of the two aromatic parts
(i.e., along −NN− or N−NH− bonds) that enhances
S DOI: 10.1021/acs.chemrev.7b00422
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nonradiative deactivation of the excited-state. When Sudan I is
encapsulated in NaX, NaY, and MCM41 materials, both trans-
and cis-proton-transferred isomers emit. The emission lifetimes
of confined trans- (20−35 ps) and cis-HYZ (113−184 ps)
structures are increased by 2 orders of magnitude, which is
mainly due to the spatial and electronic confinement in these
hosts.260,261 The trans-HYZ lifetime (21 ps) in MCM41, which
has a larger pore size (25 vs 13 Å for zeolites), is shorter than in
NaY (34 ps) (Figure 16).261 Similar behavior was observed for
the cis-HYZ form, whose fluorescence lifetime was longer in
NaY materials (184 ps) than in MCM41 complexes (113
ps).261
Figure 16. Fluorescence decays of Sudan I in the different meso- and
microporous materials gated at 580 nm. Reprinted with permission
from ref 261. Copyright 2009 Elsevier B.V.
On the other hand, fs-studies indicated that the photo-
isomerization process in these cages occurs by an inversion
mechanism, as the emission transients have similar dynamics
that are independent of the host size (Figure 17, panels A and
B). For the fs-emission transients of these complexes, two time
constants, 240 fs (IVR) and 1.70 ps (isomerization of the trans-
HYZ structure along N−N and/or C−N bonds), were
reported. The presence of solvent (water and dichloromethane)
in the nanochannels and different metal cations (Na+, Li+, and
Mg2+) in the framework affect the isomerization time (Figure
17C).260 In LiX and MgX zeolites, the Li+ and Mg2+ cations
slow the trans-cis isomerization process (2.8 and 2.3 ps,
respectively),260 while Mg2+ cations (MgX zeolite) presence has
a smaller effect than the Li+ one.260 These results show that the
nature of the metal cation (size and charge) is paramount to the
electronic charge density inside the host and affect the
photobehavior of the trapped dye.
Salicylaldehyde azine (SAA, Scheme 3), another diazo-
derivative, was studied in FAU zeolites.263 In dichloromethane
solutions, SAA exhibits an ultrafast ESIPT reaction (80 fs) that
leads to a K*-type tautomer having an emission lifetime of 55
ps.263 The Z form of SAA is stabilized in NaX zeolites in
dichloromethane in both the S0 and S1 states to the point that
no ESIPT reaction occurs.263 In the SAA/NaX complexes, the
Z* fluorescence decays exhibit a triexponential behavior (0.18,
0.9, and 2.8 ns) that is slower than SAA’s fluorescence in
solution, which is mostly because the twisting motion of the
confined structures is hindered.263 The fluorescence lifetime
values significantly depend on the SAA concentration in these
complexes (Figure 18).263
The presence of three fluorescence lifetimes and their
dependence on the dye concentration were explained by either
the caged SAA structures having different locations or by a self-
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Chemical Reviews
Figure 17. (A and B) Femtosecond emission transients of Sudan I in NaX, NaY, and MCM41 hosts in n-hexane suspensions. (C) Femtosecond
emission transients of Sudan I in MX (M = Na+, Mg2+, and Li+) in neutral water gated at 620 nm. Reprinted from ref 260. Copyright 2009 American
Chemical Society.
Figure 18. Effect of the used initial SAA concentration (in the
synthesis of the SAA/NaX composite) on the fluorescence decays
observed at 480 nm. Reprinted from ref 263. Copyright 2010
American Chemical Society.
quenching process. To analyze the quenching effect, the
fluorescence decays were fitted to a stretched-exponential
function.88,90−92 This function is also used in modeling EnT
processes presented in section 2.2.3. Upon decreasing the SAA
concentration in the composites, the characteristic time of the
decay, τs, changes from 0.19 to 1.67 ns, while the heterogeneity
parameter α increases from 0.46 to 0.61. The shortening in the
emission lifetime indicates possible interaction and EnT
between neighboring caged SAA molecules.263 Therefore, the
multiexponential behavior of the Z* tautomer can result from
the formation of different populations inside the NaX cavity
and/or from different interactions between caged SAA
molecules. The confinement effect of NaX on SAA is also
reflected at the femtosecond scale: the ultrafast IVR (∼300 fs),
VR/cooling (∼5 ps), and twisting motion (∼10 ps) are slower
than those in dichloromethane solutions (∼100 fs, ∼1 ps, and
∼5 ps, respectively).263 The salicylideneaniline derivative (E)-2-
(2′-hydroxybenzyliden)amino-4-nitrophenol (HBA-4NP,
Scheme 3) behaves similarly to SAA in the presence of FAU
zeolites, NaX, NaY, and mesoporous materials such as MCM41
and Santa Barbara amorphous (SBA15) type material.264−267 In
dichloromethane solutions, HBA-4NP undergoes an ultrafast
ESIPT reaction (∼70 fs) that leads to a K*-type tautomer with
a short lifetime (14 ps).266 The photoproduced K* undergoes a
rotational process (∼4 ps) toward nonemitting structures.266
When HBA-4NP interacts with SBMs, the shape and position
of the features in the absorption and emission spectra, as well as
the fluorescence lifetimes, show a large dependence on the dye
concentration (Figure 19).
The analysis of the data suggests the presence of monomeric
or H- and J-aggregate caged E structures that undergo ESIPT
reactions.264−267 The fluorescence lifetime of the trapped K*
monomers (∼6 and ∼2 ns for zeolites and mesoporous hosts,
respectively) is longer than that in dichloromethane (14 ps)
T DOI: 10.1021/acs.chemrev.7b00422
Review
Figure 19. Emission decays of dichloromethane solutions containing
HBA-4NP interacting with NaY using (1) concentrated (2 × 10−3 M)
and (2) diluted (2 × 10−7 M) initial HBA-4NP solutions, observing at
500 nm. Reprinted from ref 264. Copyright 2014 American Chemical
Society.
due to a hindering of the nonradiative pathways.264,265 On the
other hand, the relative populations and emission lifetimes of
H- and J-aggregates (∼100 and ∼600 ps, respectively) were
found to depend on several factors such as the loading
efficiency, the initial concentration of the dye used to make the
complexes, cavity (or pore) size, and the Brunauer−Emmett−
Teller (BET) surface area of the materials.264,265 For
microporous materials, HBA-4NP exhibits larger aggregates
formation in NaY than in NaX due to the higher loading of the
former (90 vs 20%, respectively), which is related to the lower
content of sodium cations and aluminum atoms in the zeolite
framework.264 For the mesoporous materials, whose pore size
(25 Å) is larger than that of zeolites (13 Å), higher loading (85
and 95% for MCM41 and AlMCM41, respectively), and thus
more aggregates formation was observed.265 However, within
SBA15 host (pore size = 60 Å), there is less aggregates
formation (40%) due to its weak loading ability, which is
related to its BET surface area (780 m2/g for SBA15 vs 1000
m2/g for MCM41).265 Figure 20 illustrates the different loading
of MCM41 and SBA15 materials. For complexes having a low
loading efficiency (NaX and SBA15 hosts), the caged
monomers are the predominant guest.264,265 In contrast, for
complexes resulting in a high loading efficiency (NaY, MCM41,
and AlMCM41 hosts), H- and J-aggregates are more commonly
formed, with the latter being predominant in the presence of Al
atoms.264,265 This result demonstrates that depending on the
structural and topological properties of the SBMs, different
encapsulated species of HBA-4NP might be formed.265 The fs-
photobehavior of these complexes also depends on the
host.266,267 For the NaX and SBA15 composites, the ultrafast
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Chemical Reviews Review

Figure 20. (A) Schematic representation (not in scale) of the energetic diagram at ground (S0) and electronically first excited (S1) states of
monomer (M) and H- and J-aggregates of HBA-4NP interacting with mesoporous materials in dichloromethane suspensions. For simplicity, the (S0)
and (S1) energy of the three caged structures are put at the same level. (B) Cartoon illustrating the caged structures (M and H- and J-aggregates)
within MCM41/AlMCM41 and SBA15 materials. The fluorescence lifetime for each specie is indicated in the scheme. Reprinted with permission
from ref 265. Copyright 2016 Elsevier B.V.

dynamics are dictated by the encapsulated monomers, similar
to those observed in viscous triacetin solvent, while for NaY,
MCM41, and AlMCM41, it is rather due to the aggregates,
which photodynamics is slower than in solution.266,267 For
these hybrid composites, a larger amount of HBA-4NP caged
inside the host leads to guest−guest interactions that, along
with the restriction of twisting motion, slow the guest’s global
ultrafast events such as IVR and VR/cooling processes. In the
mesoporous MCM41 and AlMCM41 complexes, the dynamics
are slower than those in microporous NaY due to the wider
space and higher content of OH-groups in the former, which
result in a larger number of specific interactions.267
Hydroxyflavones are another family of molecules that
undergo ESIPT reactions. Among them, 3-hydroxyflavone (3-
HF, Scheme 3) has drawn particular attention since its
spectroscopy depends on its surroundings, and it may be
used in several fields of science and technology.97,105,274 While
in aprotic and apolar solutions, it undergoes an ESIPT reaction
in the photoexcited neutral (N*) form to produce the tautomer
(T*), and in protic and polar solutions, the formation of T* is
inhibited by the formation of intermolecular H-bonds with the
solvent.274,275 Several studies have reported on 3-HF in the
presence of caging media as micelles,268 CDs,269,270 sol−gel
glasses,276,277 and liposome membranes.278,279 Upon excitation
of 3-HF in micelles, an equilibrium is reached between the N*
and T* species reflecting a reversible ESIPT reaction.268 In
these hosts, 3-HF exhibits the same behavior as in the H-
bonding solvents, such as methanol and water, indicating strong
specific interactions between the dye and the micelle.268 In γ-
CD, a more hydrophobic medium, an ESPT reaction produces
an excited anion (τAN = 2.14 ns).269 The deprotonation occurs
in the cavity because of specific interactions (H-bonding
network) between the dye, CD, and adsorbed water
molecules.269 The hydrophobic effect imposed by the inside
γ-CD cavity enhances and stabilizes the photoproduced caged
U DOI: 10.1021/acs.chemrev.7b00422
anion form of 3-HF.269 However, within polar and protic
zeolites such as β- and HZSM-5, the encapsulated 3-HF does
not transfer protons and only the fluorescence of the
encapsulated N* form was observed.271,272 However, in aprotic
and polar materials such as NaZSM-5 zeolites, both N* and T*
structures are present in the excited state.271 Time-resolved
diffuse reflectance spectroscopy showed that the fluorescence
lifetimes of N* and T* species are very long, with values of 165
and 746 μs, respectively.271 However, when 3-HF interacts with
polar and aprotic materials such as silicalite-1, it does not
interact with the channel walls, and T* is the only observed
species (τT = 500 μs).271
The number of reports discussed in the PT section shows the
importance of the nature of the SBMs when studying the
spectroscopy and dynamics of a PT dye. The interaction
between both entities can be specific or nonspecific, leading to
caged monomers, anions, cations, keto forms, zwitterions, and
aggregates. The diversity of these composites is reflected in
their photodynamics and spectroscopy, which greatly help the
understanding of many host−guest systems in both the ground
and excited states. In general, the observed caged photo-
dynamics is longer than that in solution.
3.2. Electron-Transfer Reactions
Photoinduced electron-transfer (ET) reactions are one of the
fundamental processes in physics, chemistry, and biology.280,281
They have been extensively studied both theoretically172,282−284
and experimentally.2,35,37,41,42,285 The standard theoretical
model that describes ET reactions was developed by Marcus
and proved a relation among the difference in the Gibb’s free
energy (ΔG) between an electron donor (D) and acceptor (A),
the curvature of the PES, and the reorganization energy.283,286
According to Marcus theory, the energies of the electron D and
A states are adjusted to match by energy fluctuations that are
caused by the surrounding media. ET can occur between D and
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Chemical Reviews
Scheme 4. Molecular Structures of the Molecules Interacting with SBMs and Discussed in the Electron Transfer Section 3.2
A in separate molecules (intermolecular) or between distinct D
and A regions within the same molecule (intramolecular). In
such inter- and intramolecular processes, the reaction products
are usually called the charge-separated (CS) and ICT states,
respectively.2,41,287,288 The stability of both states and the value
of the ET rate constant also depend on the properties of the
medium that surrounds the molecular system. Several reviews
have been published on theoretical and experimental studies on
the photoinduced dynamics of electrons (charge) transfer
within chemical and biological sys-
tems.2,4,7,27,32,34,37,41,172,173,281,287,289,290 The most recent review
gives a detailed analysis of these events in solutions and helps
the reader to understand the state-of-the-art in this field.32
Encapsulation by hosts (such as micelles, CDs, proteins, and
other molecular pockets) may change reaction paths and the
related products. Therefore, in this section, we will focus on the
effects of SBMs (as hosts) on reaction dynamics of ET and
V DOI: 10.1021/acs.chemrev.7b00422
Review
discuss the key properties of these hosts that govern the rate
constants and subsequent processes.
3.2.1. Intramolecular Charge-Transfer Reactions.
3.2.1.1. Dependence of ICT Reactions and Solvation
Dynamics upon Encapsulation in Silica-Based Materials.
Molecules with electron D and A groups in their structures
exhibit ICT reactions upon excitation. These reactions
subsequently induce changes in the electron distributions,
dipole moments, and possible conformations at the excited
state.36,41,287,288,291 The ICT rate constant in the molecular
system under consideration depends on the polarity of the
surrounding, and the specific and nonspecific interactions with
the medium.292−295 As we are concerned here with the
confinement effects of SBMs, a change in the local environ-
ment, such as polarity, H-bonding ability or cavity/pore size is
expected to affect the ICT reaction dynamics and products. In
basic media, HBO (Scheme 3) undergoes an intermolecular
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Chemical Reviews
Figure 21. (A) Schematic representation of coumarin dyes interacting with silica−surfactant complexes. Reprinted from ref 312. Copyright 2006
American Chemical Society. (B) Schematic illustration of the mesostructured silica nanochannels containing alumina membrane to encapsulated
C153. Reprinted from ref 316. Copyright 2008 American Chemical Society.
ESPT reaction with the host to produce an anion by the
deprotonation of its OH group (section 3.1).213 The presence
of the negative charge in this structure causes an ICT reaction
which time depends on the surrounding medium.213 In alkaline
methanol solutions, where the HBO anion (AN) already exists
in S0, the photoinduced ICT process occurs in 1.2 ps. When
HBO is trapped within NaX and NaY zeolites, it forms an
encapsulated AN.213 Upon excitation, the confined AN*
undergoes an ICT in 2.5 ps.213 The reaction time in zeolites
is slower than in methanol due to the higher polarity of the
local zeolite environment and the electrostatic interactions of
AN* with the aluminosilicate framework and sodium cations in
its cages.213 HPTS (Scheme 3), which has been discussed in the
previous section, is a well-known photoacid in the field of
photoinduced PT. It has been studied in solutions and in
chemical (CDs and micelles) and biological hosts.186,188−191 In
aqueous solutions, in addition to an ESPT reaction, the ultrafast
dynamics of HPTS involves two steps of 300 fs and 3 ps, which
are assigned to solvation of the locally excited (LE) state and
ICT processes, respectively.39,174,176,296,297 When HPTS is
encapsulated in γ-CD, these processes slow down, with a LE
relaxation and ICT times of 800 fs and 8 ps, respectively.
Trapped in HSA protein and ionic liquid mixed micelles, similar
behaviors were observed; and ICT dynamics slowed down to
10−200 ps.190,191,298,299 When HPTS interacts with dried
MCM41 materials, it does not exhibit any proton- or charge-
transfer processes.186 Aggregates formation was observed in
formed composites, characterized by a broad emission band
and a multiexponential behavior of the emission decays (120
ps, 600 ps, and 2.2 ns).186 However, the presence of water (1%)
in HPTS/MCM41 samples decelerates both processes. Under
such wet conditions, the LE relaxation and ICT dynamics
exhibit times of 0.8 and 5 ps, respectively.186 This retardation is
due to (i) the nature of adsorbed water molecules on the
MCM41 surface, (ii) the electrostatic interactions of the dye
with the MCM41 surface, and (iii) the decrease of freedom of
adsorbed HPTS and water molecules.186 Several studies have
shown that adsorbed and/or encapsulated water molecules
have different dynamics than those observed in bulk water
solutions.46,47,300,301 The molecular restriction to move on the
surface affects the polarity and dielectric constant of the solvent,
resulting in a deceleration of their dynamics.44,46,47,300−303 The
origins of this process are also discussed in the theoretical
section of this paper (section 2.2.1). On the other hand, the
adsorption of HPTS and its interaction with the MCM41
W DOI: 10.1021/acs.chemrev.7b00422
Review
surface also influence the electronic distribution in the dye, thus
affecting the ICT time.186 The above reports on HBO and
HPTS demonstrate the influence of the interaction with SBMs
on ICT processes. The deceleration of the ultrafast processes
changes the overall behavior of encapsulated guests, which
could affect the subsequent reactions and formed photo-
products.172,173,186,190,191,298,299,304
Molecules having electron D and A groups are often very
good probes to study solvation dynamics because their dipole
moments significantly change upon excitation. Therefore, such
molecules were also employed to study solvent reorganization
dynamics after interaction with SBMs by time-resolved
fluorescence methods. In bulk solvents, the solvation process
is usually described as consisting of a sub-100 fs Gaussian
inertial component and single- or biexponential longer decay
components of 1−10 ps duration.305 The theoretical works
about solvation dynamics in nanoconfining silica-based environ-
ments were commented in section 2.1, while here, we will
comment on and discuss the experimental findings.
The studies before 2005 of solvation in silica materials were
limited to dyes interacting with sol−gel glasses.306−308 For
example, this type of material was used to explore the solvation
dynamics of Coumarin 480 (C480), Nile Blue (NB), and C153
(Schemes 3 and 4).306−308 Generally, the solvation dynamics in
confined media (10−50 Å pores diameter) showed non-
exponential behavior of the emission decays, similar to that in
the bulk, but all time components were slowed down. However,
the time constants of the solvation dynamics in these confining
media were found to be 100−200 ps,306 which is still
approximately one order of magnitude faster than in CD
(∼1200 ps)309,310 and micelles (∼2400 ps).311
As such, much slower solvation dynamics was observed in a
mesostructured silica−surfactant nanocomposite.312 Three
coumarin dyes were studied: two of them were located in the
vicinity of the ionic interface [coumarin 343 (C343) and
C480], while the third one (propylamide coumarin 343
[PAC343], Scheme 4) was found in the hydrophobic interior
of the micelles (Figure 21A). The longest solvation time
constant is 7.5 ns for C480 and 7.6 ns for C343, while for
PAC343 (with a smaller overall Stokes shift) it is significantly
shorter: 4.8 ns. The different behavior for PAC343 were
explained on the basis of a smaller contribution of the water−
ion interaction at the ionic interface and fewer water molecules
trapped in the hydrophobic core of the micelles. A similar
nanocomposite was studied using 4-aminophthalimide (4AP)-
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
Figure 22. (A) Schematic representation of the O−H interaction of water with charged and neutral silica surfaces. τ1 is the interfacial O−H
vibrational lifetime. Reprinted from ref 320. Copyright 2009 American Chemical Society. (B) Variation of τ1 as a function of surface charge (pH 2−
12) at different material interfaces. Reprinted from ref 322. Copyright 2017 American Chemical Society.
based molecule as a solvation probe (Scheme 4).313 The probe
was made from a 4AP fluorophore and a 16-membered
hydrocarbon chain. The fluorescence spectrum indicates that
the 4AP moiety resides in the silica−surfactant interfacial
region, with the hydrocarbon tail extended into the hydro-
phobic core of the nanocomposite. Time-resolved studies
revealed fast and slow solvation components: 290 ps and 1.75
ns. These times are longer than those in cetyltrimethylammo-
nium bromide (CTAB) micelles (100 and 380 ps)314 but
comparable to those in reverse micelles (340 ps and 5 ns).315
The constrained water molecules near the ionic interface of the
micelles inside the nanocomposites were found to be the
primary contributor to the dynamics, although the slow
dynamics exchange of the free and bound water molecules
could also have a significant influence.
C153 was used to probe solvation dynamics in alcohols of
various alkyl chains confined in silica.316 Two mesoporous silica
nanochannels [calcined-nanochannel-containing alumina mem-
brane (Cal-NAM) and trimethylsilyl-nanochannel-incorporated
alumina membrane (TMS-NAM)] were fabricated inside the
pores of an anodic alumina membrane (Figure 21B). The
average solvation times are approximately 10% longer in TMS-
NAM than in Cal-NAM. The solvent relaxation times in the
nanochannels are 2−3 times slower than in alcohols with a
short alkyl chain (ethanol and 1-butanol). Interestingly, for
alcohols with a long alkyl chain (1-hexanol and 1-decanol), no
differences were observed with the confined solvation
dynamics. To explain the results, the authors proposed the
formation of rigid alcohol chains for ethanol and 1-butanol by
means of strong H-bonding interactions and less strong Van
der Waals interactions between alcohol molecules.316 In
contrast, the alcohols with a long alkyl chain were considered
to form a loose structure inside the silica nanochannels.
Solvation processes were also considered for the nano-
confined molecules for which deactivation processes other than
ICT contributed to the excited-state dynamics. In such systems,
the isolation of pure solvation dynamics is often complicated.
For Sudan I (Scheme 3), a dye showing proton-transfer and
isomerization reactions at S1, trapped in zeolites and MCM41,
the overall increase in the observed emission lifetimes (with
respect to that in the bulk) was explained in terms of a
cooperative effect of confinement (restriction to twist) and
solvation within the pores/channels.260 For HBO anions
(Scheme 3), the solvation dynamics in bulk solvents were
extracted. Upon confinement in NaX and NaY zeolites,
additional processes related to the formation of anionic forms
at S1 complicated the interpretation of the observed fs−ps
X DOI: 10.1021/acs.chemrev.7b00422
Review
behavior.213 For Nile Red (NR, Scheme 4), the combined ICT
and solvation dynamics are even shortened from approximately
1 ps in bulk dichloromethane to 200−400 fs in dried XMCM41
(X = Si, Al, Ga, Zr, and Ti).227 The increase in the environment
polarity decreases the height of the energy barrier between the
LE and ICT states, leading to more efficient formation of the
ICT form.227 Moreover, the ICT reaction dynamics also
depends on the presence of different acid sites (Brønsted and
Lewis character) in the MCM41 framework; these acid sites are
the products of doping the framework with different
metals.227,292 For example, when NR is inside MCM41,
AlMCM41, and GaMCM41 (containing Brønsted acid sites),
the ICT reaction occurs within 320−410 fs and a VR/cooling
process within 3.2−3.5 ps.227 When NR is trapped in
ZrMCM41 and TiMCM41 hosts (containing Lewis acid
sites), its ICT state is generated in less than ∼200 fs and is
later depopulated by an electron-injection (EI, in ∼250 fs)
process to reach trap states that are formed by the d-orbitals of
the doping metals.227 NR has been also studied in both β-CD
and surfactant aerosol-OT [sodium bis(2-ethylhexyl) sulfosuc-
cinate, AOT] reverse micelles in solutions, in which its ICT
process is 2.5 and 8 times slower than that in bulk water,
respectively.317,318 For these systems, the observed slowing was
attributed to the polarity of the caged water molecules being
lower than that of the bulk.317,318 The above studies are
commented about in other sections of this review (sections
3.1.2 and 3.1).
The ultrafast components of solvation are partially related to
the vibrational dynamics of solvents. Sum frequency generation
was shown to be a useful tool to study the vibrational spectra of
the water molecules at interfaces.319 Recently, experiments
using this technique with femtosecond time-resolution were
used to explore the vibrational dynamics of water at different
interfaces.320−322 The vibrational lifetime τ1 of the water O−H
stretch at silica interfaces was found to strongly depend on the
pH.320 At pH > 10, most of the surface silanols are
deprotonated, leading to a strong interfacial electric field.
Under such conditions, τ1 values were found to be similar to
those in bulk water, approximately 250 fs. This similarity was
shown to be a consequence of probing near-interface water,
whose contribution was screened in the presence of excess ions.
In contrast, for pH = 2, the surface charge density at the silica/
water interface is known to be close to zero, and at such
conditions, the vibrational lifetime increases to 570 fs (Figure
22A). The primary reason for the longer vibrational lifetime of
O−H at the H2O/silica interface at the neutral surface was
attributed to a decrease in the density of states of the low
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Chemical Reviews Review

Figure 23. Schematic representation of the photodynamics of NR interacting with Ti-AlMCM41 materials of different metals (Al and Ti) doping in
dichloromethane suspension. Reprinted with permission from ref 226. Copyright 2016 Royal Society of Chemistry.

frequency modes due to incomplete solvation of the first layer the presence of SiO2 nanoparticles in dichloromethane
of interfacial water molecules. The thermalization time constant suspensions, the emission lifetimes (∼180 ps, ∼ 800 ps, and
is similar at both low (700 fs) and high (800 fs) pHs. ∼2.5 ns) and its ultrafast dynamics (1.8 ps) are similar to those
Interestingly, a different behavior was observed at alumina observed in neat solutions, reflecting its weak interaction with
interfaces, for which the point of zero charge (PZC) occurs at this material (Figure 24A).323
intermediate pHs (6−8) than for silica.322 The vibrational
dynamics of the O−H stretch of the charged alumina/water
interface is faster than in bulk water and at a charged silica
surface (Figure 22B). The addition of excess ions was found to
have little or no effect on the time range of the vibrational
dynamics, in contrast with the behavior observed at the silica
surface.322
3.2.1.2. Electron Injection to/from Silica-Based Materials
Containing Metals. NR shows strong solvatochromism as a
result of an ICT reaction accompanied by a twisting
motion.226,227,292,293,295,317,318 This classical dye exhibits a
different behavior when interacting with tri- (Al- and
GaMCM41) and tetravalent (Ti- and ZrMCM41) metal-
doped MCM41 materials, which is related to the presence of
different types of unoccupied orbitals.227 These unoccupied d-
orbitals in Ti- and ZrMCM41 results in an EI process from the
ICT state of NR not happening in Al- and GaMCM41 hosts.
The result agrees with those of reports in which X- and Y-
zeolites (faujasites) doped with transition metals also efficiently
form trap states thanks to their d orbitals, increasing the
catalytic activities of these materials.9,227 Interestingly, when
NR was encapsulated in co-metal-doped mesoporous materials
that have two different metals in their framework (Ti-
AlMCM41), its photobehavior depends on the numbers of
the Brønsted and Lewis acid sites.226 In Ti-AlMCM41 materials Figure 24. Comparison of the fs-emission transients of TPC1
with 1% codoping of Ti and Al, an ICT process of ∼300 fs was interacting with (A) silica and MCM41, (B) Ti-nanoparticles, and
recorded.226 At this doping level, the EI process to the trap Ti-containing mesoporous materials in dichloromethane solutions.
states was not observed.226 In contrast, when the material is Reprinted from ref 323. Copyright 2011 American Chemical Society.
doped with 3% Ti and 1% Al, the ICT state forms in <200 fs
and is followed by an EI process in ∼200 fs (Figure 23).226 The However, for the TPC1/MCM41 composites, an emission
observed changes are directly related to the Ti-content in the quenching was observed in addition to the lifetimes of weakly
MCM41 framework, and the effect could be of relevance to the interacting dye molecules. The quenching is assigned to
photocatalytic activity of this material.226 intermolecular singlet−singlet annihilation between TPC1
Another electron D/A molecule that was also studied in molecules that are closely packed in the nanochannels of the
SBMs is the triphenylamine dye (TPC1, Scheme 4).323 This mesoporous materials.323 TPC1 has also been encapsulated in
molecule has been used as a light absorber in a dye-sensitized TiMCM41 (3% Ti) and TiSBA15 (SBA15 with small titanium
solar cell, and it contains electron D (triphenylamine unit) and nanoparticles within its hexagonal mesoporous structure).323
A groups (cyanoacrylic acid) in its structure.324,325 The The dynamics of the TiMCM41 and TiSBA15 complexes differ
interaction of TPC1 with MCM41 and amorphous silica from those of TCP1 interacting with SiO2 and MCM41 (Figure
nanoparticles (SiO2) was reported.323 Excited TPC1 in 24). For the TiMCM41 composites, an efficient fluorescence
dichloromethane solutions shows two lifetimes, 800 ps and quenching process occurs due to EI from the excited dye into
2.5 ns, assigned to the normal and anion forms, respectively. In the conduction band of titania domains.323 The EI reaction
Y DOI: 10.1021/acs.chemrev.7b00422
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Chemical Reviews
Figure 25. Comparison of fs-emission transients (gated at 700 nm) of a dichloromethane suspension containing TPC1 interacting with (A) alumina
particles of different size and at different concentrations of the dye and with Al-doped material and (B) different metal oxide nanoparticles. Inset:
illustration of TPC1 attached to metal oxide nanoparticle surface. Reprinted from ref 327. Copyright 2011 American Chemical Society.
exhibits a multiexponential behavior with times ranging from
300 fs to 30 ps, and an average rate constant of 2.7 × 1012 s−1
when the emission is gated at 600 nm and 1.5 × 1012 s−1 when
recorded at 700 nm.323 These rate constants are 2−3 times
larger than those in the TiSBA15 materials, indicating a
stronger coupling between the dye and titania domains in the
TiMCM41 hybrid material.323 This behavior is comparable to
the case in which TPC1 interacts with the classical titania P25
(Figure 24B).323 This phenomenon led to the study of the
interaction of TPC1 with TiMCM41 in complete dye-
sensitized solar cells.326 In such cells, the EI process was
found to be approximately 3 times slower than in a typical solar
cell configuration with P25. Unlike NR, TPC1 also exhibits an
ET reaction in AlMCM41 materials.327 This reaction occurs in
1.5 ps, and it reflects the interaction between the dye and the
Brønsted acid sites of the AlMCM41 framework that are
generated by the Al atoms.327 TPC1 has an even slower ET
reaction (150 ps) when it interacts with Al2O3 nano- and
microparticles (Figure 25A). The difference is explained in
terms of a change in Al-orbital configurations in MCM41 and
Al2O3 nanoparticles. Replacing the Si atoms with isomorphic Al
ones introduces a Brønsted acid site that in turn increases the
electron-accepting ability of the MCM41 frameworks and
hence accelerates the ET reaction.327 In other nanoparticles
that are of interest of photonics [e.g., solar cells, light-emitting
diodes (LEDs), and photocatalysis] such as ZnO and ZrO2, the
EI process is faster (4 and 11 ps, respectively) than that in the
Al2O3 ones (Figure 25B).327 The involved kinetics is directly
related to the conduction band (CB) energy of these oxide
nanoparticles.327
This phenomenon was also observed when a zinc-porphyrin
(YD2-o-C8, Scheme 4) was trapped in layers of titania and
alumina NPs.328,329 In the presence of titania, YD2-o-C8
exhibits an ultrafast EI process through a CS state that leads to
efficient fluorescence quenching. However, this process does
not occur in alumina because its CB lies approximately 4 eV
above that of titania.329−331 Therefore, for YD2-o-C8/Al2O3
nanoparticles, only an ICT state whose formation is faster in
the presence of nanoparticles (500 fs) than in acetonitrile
solution (2 ps) was observed.328 These results provide
information about the interaction of this dye with the
semiconductor NPs, which are of interest to solar cell
applications (see also section 5.3).
Metal phthalocyanines (MPc) are an attractive class of
molecules that are known for their strong absorption in the
visible region, easy synthesis, flexibility in their molecular frame,
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and numerous applications such as semiconductor devices,332
photovoltaics solar cells,333,334 chemical sensors,335,336 and
optoelectronic devices.334,337 The spectral properties of MPc
can be modified by encapsulation or by a covalent linking
within nanochannels, resulting in interesting composites for
solar energy conversion. Palladium phthalocyanine (PdPc) has
been studied in the presence of MCM41 materials.338 The
samples were prepared either by diffusion of the dye in
dichloromethane suspensions into the mesoporous material
(PdPc/MCM41) and/or covalent bonding (MO-PdPc) to its
framework.338 The absorption and emission spectra of PdPc/
MCM41 are similar to those of PdPc complexes. However,
when PdPc is covalently bonded to MCM41, both absorption
and emission spectra are red-shifted, reflecting a change in its
photobehavior. This response is also manifested in the
fluorescence lifetime of the composites in dichloromethane
suspensions. For PdPc and PdPc/MCM41 samples, lifetimes of
20 ps and 2.4 ns were observed; while for MO-PdPc samples,
decaying components of 20 ps, 5.8 ns, and 1.4 ns were
recorded.338 The 20 ps component is due to intersystem
crossing (ISC) to the triplet state, which is enhanced by Pd
atoms and is common in MPc photochemistry. The second
component is assigned to emission from a photoproduct that is
formed by a photoinduced metal EI process making this
generated species living longer when the PdPc is covalently
linked to the host (5.8 for MO-PdPc vs 2.4 ns for PdPc/
MCM41). The 1.4 ns component, which is not observed in
PdPc and PdPc/MCM41 complexes, is suggested to be due to a
different population of PdPc molecules having established
specific interactions with the mesoporous framework. The
results of the femtoseconds study show evidence for two
processes in the ultrafast regime: a 170−500 fs component
assigned to IVR, internal conversion, and photoinduced loss of
Pd ions and a 1.5−4.4 ps component due to VR/cooling
processes.338 Therefore, the study shows that covalently
bonding PdPc to the host redshifts the absorption and emission
spectra, affects its dynamics, giving a metal-ejected photo-
product and forming a population based on its specific
interactions with the framework.
Another aspect of the overall ET reactions to consider in any
system is the back ET that may happen (or electron
recombination). In accordance with Marcus theory, solvent
reorganization enhances back ET reactions.280 The time
constants of this back reaction in solutions are from
femtoseconds to hours or days depending on the kind of
system under study and surrounding conditions. The
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Figure 26. Cartoon illustrating proposed photoinduced processes of the radical cation of t-St trapped in zeolites cages showing: (A) charge
separation and direct charge recombination and (B) charge separation, electron−hole recombination, and hole transfer to the material. Reprinted
from ref 341. Copyright 2012 American Chemical Society.
encapsulation of dyes in SBMs decreases the probability of this
reaction.28,91,326,339−351 Trapping an electron D−A molecule in
SBMs retards the back ET, effectively enabling the photo-
generation of long-lived CS species. For example, when the 9-
mesityl-10-methylacridinium ion (Acr+-Mes, Scheme 2) is
incorporated into AlMCM41 materials (Acr + -Mes/
AlMCM41), nanosecond time-resolved absorption and electron
spin resonance (EPR) experiments on the solid-state samples
indicated the formation of an extremely long-lived ICT state
(10 s, Acr • -Mes •+ ). 342,352 The femtoseconds transient
absorption spectra of Acr+-Mes/AlMCM41 composites reveal
an ICT reaction with a rate constant of 3.4 × 1011 s−1, which is
slightly lower than that observed for Acr+-Mes in acetonitrile
solutions (5.8 × 1011 s−1).342 Similar behavior was observed in
1,6-diphenyl-1,3,5-hexatriene (DPH, Scheme 4) molecules that
are encapsulated in sodium-exchanged ZSM-5 zeolites, having
the formula Nan(SiO2)96‑n(AlO2)n (n = 60.6 or 3.4), which are
denoted NanZSM-5.353 DPH is known for its fluorescence
properties and particularly for its use as a probe in biological
membrane studies.354−356 Upon adsorption of DPH in
Na n ZSM-5 zeolites and photoionization, its CS state
(DPH•+/NanZSM5•−) is stabilized and exhibits a long lifetime
(minutes). This lifetime depends on the temperature, and the
content and distribution of the Al atoms in the zeolite
structure.353 For DHP/Na6.6ZSM-5 composites, the CS state’s
lifetime ranges from 3850 min at 293 K to 8 min at 353 K,
while for DHP/Na3.4ZSM-5, the lifetime changes from 65 min
at 293 K to 3 min at 353 K. This difference reflects the key role
of both the temperature and aluminum content in the DHP•+
electron recombination process.353 When trans-stilbene (t-St,
Scheme 4) is trapped in zeolite cages, it also has a long-lived
CS, one that stays for hours.341,357,358 Within the channels of
nonacidic-doped ferrierite, mordenite, and inverted mordenite
zeolites [M-FER, M-MOR and M-MFI, respectively where (M
= Na+, K+, Rb+ and Cs+)], a photoinduced intermolecular ET
reaction was observed in t-St.341,358 In these composites, the
back ET process includes direct charge recombination (CR),
hole transfer (HT), and electron−hole recombination to
reform the caged t-St (Figure 26).341
The CS state lifetime depends on the caging zeolite (FER,
MFI, and MOR) and the nature of the extra framework cation.
When t-St•+ is trapped in the K-FER, K-MFI, and K-MOR
zeolites, its lifetime decreases from 10 h to 20 min and 0.4 s,
respectively.341 This difference is related to a restriction to
move in these hosts and thus governed by the size of the cages,
being smaller for FER (pore size dimensions = 0.42 × 0.52
nm2) than for MFI (0.53 × 0.56 nm2) and MOR (0.67 × 0.76
nm2). In FAU, zeolites having a large supercage (1.3 nm in
diameter), the t-St•+ lifetime is 150 μs.359 Interestingly, the CS
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lifetime also decreases with the increasing size of the alkali
metal cation (M+). For example, in M-MFI composites (M =
Na+, K+, Rb+, and Cs+), the lifetime decreases in the following
order: Na+ (22 min) > K+ (20 min) > Rb+ (16 min) and Cs+
(12 min). However, interacting with zeolite beta shows a
different behavior.340 In this material, the formation of the t-
St•+ radical cation is faster than in previously mentioned
zeolites because the caged t-St has greater freedom of motion.
The lifetime of the CS state is tens of microseconds.340
Therefore, the available space inside zeolite hosts plays an
important role in stabilizing the CS states. This trend was also
observed for t-St caged in MOR zeolites doped with TiO2
nanoclusters.358 Spontaneous ionization generates a CT
complex in MOR zeolites without titania, but in the presence
of TiO2, the t-St radical (70 min) is more stable. The reduction
of the internal microporous volume that is caused by the
presence of titanium slows the charge recombination process by
the confinement effect.358 In general, the introduction of ET
molecules into the restricted spaces of zeolites and mesoporous
materials slows back ET reactions, which is advantageous for
the development of materials for photonic applications.
3.2.2. Intermolecular Electron-Transfer Reactions.
3.2.2.1. Encapsulated Electron Donor and Acceptor Molec-
ular Systems. The study of ET reactions has been extended to
bimolecular systems, in which two different molecules, one an
electron donor and the other as an acceptor, are encapsulated
in the material. Electron donor t-anethole (t-An, Scheme 4) and
acceptor 1,4-dicyanobenzene (DCB, Scheme 4) have been
introduced into zeolite-Y cavities and their photoevents have
been studied.360 Upon excitation of the composite, a caged
An•+ radical-cation is formed, followed by an electron migration
to the DCB molecules, which generates its radical anion
(DCB•−). In zeolite-Y samples with different metal cations (Li+,
Na+, K+, Rb+, and Cs+), the electron migration is affected by the
alkali metal in zeolite-Y framework.360 Transient diffuse
reflectance experiments yielded three distributions of rate
constants characterizing the generated pair of the radical’s
cation and anion. The fastest behavior was observed for NaY
sample, with three time constants (52 min and 9 and 75 h),
while the slowest one was recorded for RbY (220 min and 22
and 108 h).360 Thus, NaY is found to be the best zeolite to
facilitate charge separation by electron migration in photo-
excited species. Another report studied ET processes between
the electron-donor p-terphenyl (PTP, Scheme 4) and acceptor
DCB within Na-ZSM5 zeolites.357 In the absence of DCB,
photoexcitation of PTP in PTP/NaZSM-5 composites
generates PTP•+ radical-cations with a lifetime of 21 min that
evolve into an electron−hole pair in which the electron is
captured by the zeolite framework with a time constant of 653
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min (Figure 27).357 Both species are more stabilized in the
presence of DCB molecules.357 In PTP-DCB/NaZSM-5
Figure 27. Illustration of the competitive electron transfer events of
PTP to DCB dye and ZSM-5 zeolite framework. Reprinted from ref
357. Copyright 2016 American Chemical Society.
complexes, the radical-cation and electron−hole pair lifetimes
are longer (83 and 3300 min, respectively). This long-living
state is mainly due to the strong confinement that is imposed
by the ZSM-5 nanochannels and the intrinsic strength of its A
sites.357 In addition to that, both the ZSM framework and the
encapsulated DCB molecules compete for the electron
capture.357
The introduction of metal complexes, acting as electron
acceptor, into SBMs has also been extensively stud-
ied.344,348,350,361−363 In these hosts, long-lived CS states with
lifetimes from nanoseconds to seconds were re-
corded.350,361,363,364 For example, when phenosafranine
(PHNS, Scheme 4) was adsorbed in the Y-zeolite surface in
the presence of caged metal complexes of nickel(II), (Ni-
(bpy)3)2+ induced intermolecular ET processes in the nano-
seconds regime (Figure 28). Upon excitation of the composites,
the adsorbed PHNS molecules transfer an electron to the Ni
complex that is also encapsulated in the Y-zeolite supercage.364
Similar behavior was found when tris(2,2′-bipyridine)-
ruthenium(II) (Ru(bpy)32+) is trapped in Y-zeolite that is
surrounded by bipyridinium ions.350 In this complex, the
presence of bipyridinium ions increases the lifetime of the
photoexcited Ru(bpy)32+, promoting the extent of the forward
ET reaction. Moreover, the longer distance between the
encapsulated Ru(bpy) 32+ complex and the external bipyr-
idinium ions retards the back ET reaction.350 Clearly, the
distance between D and A molecules plays an important role in
this kind of reactions and can even cause its inhibition. This
Figure 28. Representation of PHNS adsorption on the surfaces of (A) NaY and (B) (Ni(bpy)3)2+ NaY. Reprinted with permission from ref 364.
Copyright 2014 Springer.
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situation was observed for Ru(bpy)32+ (acting as D) and
methylviologen (MV2+, Scheme 4) (acting as A) that were
encapsulated in clay particles of different sizes.361 ET was
observed only in the presence of small clay particles. A long-
lived CS state was also detected in the caged [(bpy)2RuLDQ]4+
complex (being LDQ = 1-[4-(4′-methyl)-2,2′-bipyridyl]-2-[4-
(4′-N,N′-tetramethylene-2,2′-bipyridinium)]ethene)) and ad-
sorbed MV2+ in zeolite.363 In this system, the long-lived state
results from a competition between the slow back ET reaction
(rate constant = 3.0 × 105 s−1) and an electron migration that
moves the charge away from the surface of the zeolite, caused
by self-exchange between the densely packed MV2+ groups
(rate constant = 2.0 × 105 s−1).363 Therefore, strong
confinement effects and an internal electrostatic field contribute
to the deceleration of the CR process and stabilize the
photoinduced transient species, resulting in exceptionally long
lifetimes of several seconds to hours and even several days.
3.2.2.2. Electron-Donor Molecules Encapsulated in Silica-
Based Acceptor Materials. The encapsulation of organic
molecules that have an electron D group in their structure
can enable an ET process to the silica-based metal-doped
framework. Such a reaction was observed when 7-HQ (Scheme
3) was encapsulated in titania-doped SBMs.200 The interaction
of 7-HQ with MCM41, TiMCM41 (6% Ti doped), and purely
Ti-mesoporous (TiMeso) materials was studied at the fs−ns
regime.200 First, 7-HQ interacting with regular MCM41 results
in E forms that have different H-bonds to the host framework
and a K tautomer formation of S0. Upon electronic excitation at
the caged E form, proton transfers in these trapped H-bonded
structures to the MCM41 framework results in confined
anions.200 These dynamics were discussed in section 3.1. These
anion and keto forms can give an electron to an electron-A
partner in the host. ET was thus examined using MCM41
doped with titania.200 No ET process was observed using
regular MCM41 host, but emission quenching due to ET was
recorded in TiMCM41 (titanium-doped material with 6%
loading) and TiMeso (crystalline mesoporous all-TiO 2
structure with a uniform pore size distribution similar to that
of MCM41) (Figure 29).200
In the TiMCM41 complexes, the ET process occurs in 0.3−5
ps, while in TiMeso, the emission decays are even shorter
(Figure 29, panels B and C).200 The interaction with TiMeso
results in two different EI reactions: one from the anionic forms
(0.1−0.4 ps) and another from the Z ones (0.8−1.2 ps).200 The
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Figure 29. Femtosecond-emission transients of 7-HQ interacting with (A) R-MCM41, (B) Ti2-MCM41, and (C) TiMeso materials in
dichloromethane suspensions, gated at the indicated wavelengths. Reprinted from ref 200. Copyright 2012 American Chemical Society.
difference between EI times in the anion and Z structures is
explained by the differences in excited state energies compared
with that of the titania conduction band (Figure 30). The
Figure 30. Schematic representation of energy levels of S0 and S1 of
AN and Z forms of 7-HQ interacting with TiMeso material in a
dichloromethane suspension. The scheme shows the values of time
constants of EI to titania conduction band. Reprinted from ref 200.
Copyright 2012 American Chemical Society.
excited anions emit at wavelengths shorter than the Z emit, so
faster emission quenching of the formers was observed. When
7-HQ interacts with TiO2 nanoparticles (P25), it behaves like
in TiMeso, reflecting the strong interaction of this guest with
the titania surface of the MCM41 materials and the small
confinement effect on the EI process.200 P25 nanoparticles
were also mixed with MCM41 materials.200 In this case, the 7-
HQ interacting with the TiO2/MCM41 hybrid material showed
the same dynamics that it was recorded in MCM41.200 Due to
the large size of the used titania nanoparticles (50 Å), they are
located outside of the MCM41 nanochannels, where caged 7-
HQ barely has contact with them.200 This spatial arrangement
indicates that the ET processes in these composites needs a
direct contact between caged 7-HQ and the titania domains.
For the cases of TiMCM41, which is doped with a low amount
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of titanium atoms (6%), and TiO2-MCM41, which is doped on
the surface with large nanoparticles, some of the trapped 7-HQ
molecules are not in contact with the titania domains, resulting
in different population not all having ET with the titania sites.
However, for TiMeso materials and neat P25 NPs, which
directly contact the 7-HQ, the efficiency of the ET reaction is
higher.200
The photosensitization of TiO2 in cages or micro- and
mesoporous materials has been used as a strategy for the
formation of ET complexes. Several studies of the photo-
physical properties of PHNS (Scheme 4) adsorbed on different
zeolites and mesoporous materials that were photosensitized
with TiO2 NPs have been published.230,233,364−367 PHNS is an
azine derivative that can behave as an electron A and D in both
the ground and excited states, which makes it an important
molecule in the field of ET. When this dye is trapped within
NaY and ZSM-5 supercages, its fluorescence decays are
biexponential, with time constants of 0.48 and 1.42 ns
(PHNS/NaY) and 0.13 and 0.55 ns (PHNS/ZSM-5), which
are similar to those observed when silica nanoparticles were
used, reflecting that this molecule mostly interacts with the
zeolite surface.365 In both complexes, the presence of TiO2 NPs
causes a static emission quenching that is proportional to the
TiO2 concentration in the host.365,366 When TiO2 NPs are in
MCM41 material, they also enable an EI process from the S1
state of PHNS to the CB of the semiconductor.230 However,
the ET reaction is more efficient in the MCM41-based
complexes than in the zeolite-based ones since the
encapsulation of the dye inside of the larger MCM41 pore
allows greater contact with the TiO2 NPs, thus producing faster
EI processes.230,366 Similar studies were reported for other dyes
such as PF, Th+ (Scheme 2), and methylene blue (MB)
(Scheme 4) interacting with ZSM-5 and NaY zeolites and
MCM41 materials.230,232−234 The results show that the
photophysical properties of these dyes are affected by the
morphology and the composition of the host materials and the
presence or absence of TiO2 NPs.230,232−234 In SBMs, the
fluorescence of these molecules decay biexponentially; the short
component is attributed to the molecules that exhibit strong
interactions with the silica host, and the long one is due to
molecules whose environment is similar to the solution.232,234
The introduction of TiO2 NPs inside these hosts produces a
decrease in the fluorescence intensity attributed to the
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Scheme 5. Molecular Structures of the Dyes Interacting with SBMs and Discussed in the Energy Transfer Section (Section 3.3)
photosensitization of TiO2 by caged dye molecules through the
EI process.232,234
The reports reviewed in this section reflect how the
molecular encapsulation of dyes in SBMs improves their ET-
based photoreactions by increasing the stability of the
photoinduced CS state and preventing the back ET reaction
or making it slower. The results suggest strategies for better
designs of trapped electron D−A systems that might be used in
solar cells, photocatalysis, and molecular memory systems and
in nanophotonics in general. Some of these approaches were
used in the prototype devices described in the application part
(section 5). These strategies indicate that proper selection of
the SBMs pore size and semiconductor particle diameter can
tune the interaction in the composites toward a desired goal
such as photosensitization or stronger fluorescence of the
confined system. In addition to this strategy, the concentration
of the dye and, thus, the possible formation of aggregates within
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the host can be controlled to change the photobehavior of the
hybrid complexes.
3.3. Energy-Transfer Events
The EnT process, in which an excited D molecule transfers its
energy to A, can occur via FRET (dipole−dipole interaction)
and/or via the Dexter mechanism (electron exchange). A large
amount of works on this topic has been performed with
chemical and biological systems.5,16,94,368−380 EnT occurs in
both natural and artificial systems. Several review articles have
examined EnT in solution,32,287,380,381 in biological systems,
and hybrid materials such as zeolites, clays, and polymeric
nanoparticles.2,4,5,7,16,382−384 Recently, the photochemical and
photophysical aspects of EnT in liquid solutions and hybrid
materials have been reviewed.16,32 Ultrafast photochemical
reactions in homogeneous liquids including intra- and
intermolecular charge-transfer processes, the design of optical
artificial antennas using hybrid materials, dye-doped latex
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nanoparticles, and molecular antennas based on D and A dyes
were discussed.16,32 As we have already commented on, dyes
(D and A) can be adsorbed on the silica surfaces or within their
channels, in which the cavities of microporous and mesoporous
structures provide a D−A distance that ranges from 20 to 100
Å. At these distances, FRET processes span from the
femtoseconds to the milliseconds regime.16,88,370,375,376 To
the best of our knowledge, EnT in all the systems involving
SBMs follows FRET to occur, without any information on the
possibility of the Dexter mechanism. The confining space
afforded by the nanochannels of the mesoporous materials and
most of the zeolite structures allows dyes to orient and pack
when being encapsulated, thus promoting ways to “control”
their relative orientation and distance between different D and
A units for FRET. This consequently allows the creation and
tuning of photonic antennas that are based on
EnT.5,16,374,376−378,385−389 The related process can also
manifest when the excited encapsulated partners directly
interact with the silicate framework, thus affecting the efficiency
of other competitive processes.
In other sections of this review (related to PT, ET and
aggregates formation) that are included in section 3, the
systems under study have been classified according to the
properties of the molecules; in contrast, the EnT part has been
divided according to the materials that were used. The reason
for this classification lies in the complexity of the systems
described here; separating classes of molecules would
complicate the comment and review of the published works.
3.3.1. Energy Transfer in Dye-Doped Zeolites.
Encapsulation of organic dye molecules inside the channels of
zeolite materials enhances the stability of the dye molecules
and, in many cases, prevents aggregation and fluorescence
quenching.72,94,385,387,390−393 One of the most used zeolites in
the field of EnT is zeolite L. This material possesses a
crystalline structure that is formed by one-dimensional
hexagonal channels of 7−13 Å in diameter, making it an
appealing host for organizing highly fluorescent dyes.394,395
Geometrical constraints imposed by its pores lead to a
supramolecular organization of the guests that is ideal for
fundamental studies in unidirectional EnT.5 A large number of
studies based on the organization of dye molecules trapped in
its channels has been published.94,374−376,385,387,394−396 Some of
these studies have reported on the introduction of “stopper”
molecules that control the interaction between the zeolite-
encapsulated dyes and the outside environment.370,389 These
stoppers at the gates of the pores are selected to act as blockers,
not allowing the trapped molecules to exit. They can also be
photoactive systems such as energy donors, which, in
combination with other molecules trapped inside the channels
that act as energy acceptors, creates an efficient antenna
system.370,386,388,389,395,397,398 To study the EnT in zeolite
crystals, microporous zeolite L and two dye molecules,
pyronine B and pyronine Y (PyB+ and PyY+, respectively,
Scheme 5), were used as the host and guests, respectively.399
Polarized-fluorescence microscopy images have demonstrated
that the incorporated PyB+ molecules were forced to align
along the direction of the channel of the zeolite L crystal and
that the arrangements of the PyY+ ones were located mostly at
both ends of the channel. The study analyzed the dominant
EnT between molecules that were internally incorporated into
and externally adsorbed on the zeolite L monolayer.399 For the
case of vertically aligned PyB+-containing zeolite L monolayers
(v-PyB+/L-g)AP, the EnT from the internally incorporated PyB+
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molecules to externally absorbed PyB+ molecules is the
dominant pathway (Figure 31).399
Figure 31. Cartoon showing the difference in the energy transfer ways
in (A) (v-PyB+/L-g)AP from internally incorporated PyB+ molecules to
externally absorbed ones, and (B) (v-PyY+/L-g)AP mostly between
internally incorporated PyY+ molecules of different orientations in the
channels of zeolite L. Adapted with permission from ref 399.
Copyright 2014 Elsevier B.V.
On the other hand, the EnT in vertically aligned PyY+-
containing zeolite L monolayers (v-PyY+/L-g)AP occurs mostly
between internally incorporated PyY+ molecules that have
different orientations in the zeolite L channels. This transfer
results in an increase in the fluorescence depolarization ratio
(I⊥/I∥).399 Thus, the EnT process can be controlled by
selecting appropriate molecules. Another class of hybrid
assemblies that were based on zeolite L has also been
explored.375 In these systems, the A molecules (Ox+, Scheme
2) are organized in the channels of zeolite L, while the D
species, CdSe/ZnS QDs, are adsorbed on the surface. The QDs
absorb light and undergo electronic EnT, funneling the energy
inside the channels and providing an artificial antenna. The
mechanism for this photoinduced process is ascribed to
vectorial FRET and was demonstrated and quantified using
microscopy techniques, steady-state, and nanosecond time-
resolved spectroscopy.375 The EnT efficiency was determined
to be 70%, with a Förster distance (R0) of 73 Å and rate
constant (kEnT) of 1.65 × 108 s−1. These findings show that the
system is efficient in absorbing light and vectorially transferring
the electronic excitation energy to an acceptor located inside
1D nanochannels.375
Another strategy to get EnT process in zeolite materials was
demonstrated in an inorganic chalcogenide-based semiconduc-
tor zeolite material (denoted RWY) that served as an UV−
visible light-harvesting host.386,397 This optically active
chalcogenide-based zeolite, capable of integrating porosity
with semiconductivity and photoluminescence, provides a
new opportunity for framework-involved EnT between an
inorganic host and an organic guest. The initial multistep
vectorial EnT scaffold was fabricated by encapsulating acridine
orange into the RWY porous framework and then covering the
formed capsules with the same dye and rhodamine B molecules
(AO and RhB, respectively, Scheme 5).397 Upon excitation of
the RWY host, it transfers its energy to AO molecules and then
to RhB ones to give rise to a visible-light emission. The
photodynamic behavior was monitored getting the emission
decays of the RWY host, RWY/AO, and Rhb-(RWY/AO)
composites. Multiexponential behavior with three time
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constants was observed for the three samples.397 The average
fluorescence lifetime (3.50 ns) in RWY is longer than that in
the presence of AO molecules (3.08 ns for RWY/AO
complexes), indicating EnT from RWY to AO guest. Similar
behavior was observed when RhB molecules were added to the
above composite. Thus, two EnT events, from RWY to AO
(EnT1) and from AO to RhB (EnT2), occurred with relatively
low efficiencies (12% and 9%, respectively).397 A multistep (or
stepwise) EnT assembly based on the RWY framework was
further developed by encapsulating both pyronine and
proflavine ions (Py+ and PFH+, Schemes 2 and 3, respectively)
(Figure 32).386 The UV photons that were absorbed by the
Figure 32. Multistep energy-transfer processes in RWY/PFH+/Py+
host−guest antenna systems. Reprinted with permission from ref 386.
Copyright 2015 Royal Society of Chemistry.
RWY host were transferred to the PFH+ ions and then to Py+
ones to produce a visible-light emission. The treatment of the
guest ions after their encapsulation such as acidification of the
PFH+ ions and the solvation of the guests were also
investigated to tune the EnT efficiency in such host−guest
antenna systems. The acidification of the PFH+ guest
dramatically enhances the EnT efficiency in both steps,
increasing from 14 to 33.7% for RWY-PFH+ (EnT1) and
from 29.1 to 37.8% for PFH+-Py+ (EnT2).386 On the other
hand, solvation experiments showed that the EnT efficiency
depends on the used solvent. For example, while water is not
beneficial to EnT, organic solvents such as ethanol,
tetrahydrofuran, and toluene drastically promote the EnT
from RWY to PFH+ (EnT1) and from PFH+ to Py+ (EnT2).386
These results indicate that in addition to the structure of the
guest, the environment plays an important role in controlling
the EnT in these host−guest antenna systems.
3.3.2. Energy Transfer in Dye-Doped Mesoporous
Materials. When organic dyes are encapsulated within
mesoporous materials, efficient EnT systems can also be
formed. The ability of these hosts to encapsulate a variety of
aromatic molecules along with the ease of chemically modifying
the silica framework make them the hosts of choice for the
fabrication of nanoantenna-based composites. The encapsula-
tion can significantly stabilize the D and the A entities, thus
giving rise to more efficient FRET. The smaller space in the
nanochannels of the materials can promote molecular events
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that are not observed in solutions. Some D and A molecules in
solutions do not exhibit EnT, while, when trapped into the
pores, they show the intermolecular energy events. For
example, TPC1 (Scheme 4) fluorescence behaves normally in
solution, but upon encapsulation in MCM41 pores, it behaves
differently.323 We commented on this study in the ET section,
as TPC1 molecules transfer electrons when interacting with
titanium inside host materials (TiMCM41 and TiSBA15). In
dichloromethane solutions, two fluorescence lifetimes (800 and
2.5 ps) were observed, assigned to neutral and anion forms,
respectively. When TPC1 is trapped in MCM41, an additional
small and shorter component (180 ps) was observed and
attributed to a self-quenching by EnT.323 The origin of this
process was proposed to be singlet−singlet annihilation, which
originates from EnT between two excited TPC1 molecules.323
The strength of the interaction of a trapped guest with the
OH groups of the framework surface and the nanosized pores
of its channels can also alter the EnT between encapsulated
dyes. This has been demonstrated in a study in which the
FRET efficiency between Rhodamine 6G (R6G, Scheme 5),
acting as donor, and RhB as acceptor, was enhanced due to the
variation in the strength of interaction of both partners with the
MCM41, MCM48, and SBA15 mesoporous materials.400 The
FRET efficiency between the dyes was determined using the
ratio of the emission intensities (I0/I) in the absence and
presence of quencher (A) at different concentrations. From the
slope of the plot of I0/I (emission quenching) versus RhB
concentration, Stern−Volmer quenching constants (Ksv) were
obtained. The analysis yielded Ksv = 6.11 × 105 M−1 for
MCM48, 2.92 × 105 M−1 for MCM41, and 2.31 × 105 M−1 for
SBA15.400 Therefore, the highest EnT efficiency was observed
for MCM48 composites, followed by MCM41 and SBA15
ones.400 The EnT is enhanced in these mesoporous materials as
indicated by the larger Ksv values when compared to those in
water with a Ksv = 1.65 × 105 M−1. The three-dimensional
structure of MCM48 is the most favorable for the FRET
process since its channels can highly disperse the dye
molecules. On the other hand, the encapsulation of bulkier
dye molecules can result in pores obstruction in MCM41, thus
decreasing the EnT efficiency. Although SBA15 has a large pore
diameter (d ∼ 60 Å), which may be advantageous for the
dispersion of the guest molecules, the EnT efficiency was lower
than in MCM41 (d ∼ 25 Å).400 The authors explained this
difference as a result of a lower density of OH groups in SBA15,
which leads to a longer distance between the guest
molecules.400 The EnT efficiency can also be controlled by
modifying the framework properties with the introduction of
metal atoms (doping), as we have commented on for other
processes. The effect of doping was demonstrated for MCM48
materials having Al and Ce atoms in their frameworks.400 The
presence of these metal atoms decreases the FRET efficiency
because of an increase in the ability of the material to accept an
electron from the D molecule (R6G).400 EnT in Ce-MCM48 is
lower than in AlMCM48, and it is less efficient in both than in
regular MCM48. The results also demonstrate that EnT
between caged dyes can be regulated by doping the framework
with metal atoms of different oxidation abilities (here Al and Ce
atoms).400 Adjusting these properties enables different colors of
emission from these composites to be observed, which could be
of potential interest in photonics and sensing.
3.3.2.1. Systems with Donor Dyes Bound to a Mesoporous
Surface. Another strategy used to construct host−guest
antenna systems based on SBM composites is to directly
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Figure 33. (A) Chemical structures of TPPy-derivative organosilane precursors TPPy-Si and PBI dyes 1−4. (B) Emission quenching efficiency of the
P123-TPPy films doped with PBI dyes. Reprinted from ref 378. Copyright 2012 American Chemical Society.
dope the donor unit into the mesoporous material framework
or covalently link it to the inner walls, while the acceptor is
encapsulated within the nanochannels. Dye-doped periodic
mesostructured organosilica films with different host−guest
arrangements were fabricated and examined.378 The photo-
functional system is formed by fluorescent tetraphenylpyrene
(TPPy)-silica mesostructured films, which act as the host
donor, and perylene bisimide (PBI, Scheme 5) dye, which acts
as the guest acceptor (Figure 33A). In these composites, the
effect of different substituents in the PBI molecular structure on
the EnT process has been explored (1−4 in Figure 33A).378
In dye 1, weak fluorescence quenching due to aggregates
formation inside the mesostructured material was observed
(Figure 33B). Here, the EnT process occurs between the TPPy
moieties and the PBI dye aggregates. For dye 2, which is a PBI
derivative with bulky substituents and polar anchoring groups, a
low population of aggregates was formed, and the monomers
were the predominant species. The composite exhibits an
efficient FRET from the host TPPy to the PBI dye. Using dye
3, a mixture of monomers and aggregates species was recorded,
although self-quenching by face-to-face association was sup-
pressed due to the bulky R1 and R2 substituents (Figure 33A).
However, the FRET process was not observed since the D−A
(host−guest) distance was longer than the critical Förster
radius (ca. 4.5 nm). This host−guest arrangement is useful in
certain cases (e.g., photoluminescent materials) because the
undesired EnT is completely suppressed due to the isolation of
D and A partners. Remarkably, dye 4 exhibits the most efficient
fluorescence quenching, which is caused by a photoinduced ET
from the host, TPPy-silica, to the guest, PBI (Figure 33A). The
transient absorption experiments showed that radical (PBI•−)
generation occurs in <100 ps, and the resulting CS state lived
for nanoseconds (Figure 33B). Therefore, dyes 2 and 4 suffer
from efficient emission quenching but as a result of different
competing processes (EnT and ET, respectively).378 These
results further demonstrate the relationship between the EnT
efficiency and the guest molecular structure.
Another system with comparable architecture that exhibits
EnT comprises biphenylylene-bridged periodic mesoporous
organosilica (PMO) powder doped with coumarin 1 (C1,
Scheme 5).371,401 The picoseconds time-resolved fluorescence
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Review
spectra of the no doped Bp-PMO composites showed the
formation of three types of excimers (E1, E2, and E3), each with
different formation time constants.401 Upon excitation of Bp-
PMO, its fluorescence spectrum up to 100 ps has a peak at 330
nm, assigned to E1 (Figure 34A). From 0.1−0.2 ns to
approximately 20 ns, the fluorescence spectrum becomes
broader, and the change is attributed to the formation and
emission of E2 and E3 (Figure 34A). Interestingly, in the
presence of 0.1 mol % C1, the rapid formation of Bp excimers is
followed by an EnT to C1 in the mesochannels (Figure 34B).
From 0.1 to 0.2 ns gating time of its fluorescence spectra, a new
band at 440 nm was recorded. The emission intensity of this
band increases with time, while that of E1 decreases, indicating
an EnT from the excimers of Bp to C1. In the case of larger C1
doping (0.36 mol %), spectral changes due to excimers
formation were also detected until 0.2 ns (Figure 34C). After
on, the decay of the 365 nm emission band and rise of the 440
nm one were shorter than those in 0.10 mol % C1-doped Bp-
PMO (Figure 34, panels B and C). The excimers fluorescence
(390 nm) increased with a decrease in the monomer
fluorescence (300 nm), after which the C1 fluorescence (465
nm) increased with a decrease in the excimer fluorescence.
These results clearly indicate that the S1 state of the Bp moiety
prefers to form excimers rather than to transfer its excitation
energy to C1 (although these two processes are competitive)
and that EnT occurs after excimer formation. The Förster
radius between both sets of partners was calculated to be 3.2
nm, suggesting that other mechanisms contribute to the
observed efficient EnT. Monte Carlo simulation suggested
that FRET occurs from three types of Bp excimers to C1
molecules that are located in the vicinity of the pore surface. It
happens at the hydrophilic silica layers on the pore walls, while
some of the Bp excimers are not affected by any A.401 These
results demonstrate how the heterogeneity of the system affects
the EnT mechanism, with an emphasis on how competitive
ultrafast reactions such as excimer or aggregates formation
directly contribute to the efficient EnT process.
Mesoporous organosilica materials have also been used as
hosts for EnT systems.402 FRET was reported between 1,8-
naphthalimide covalently attached to the host and trapped
N,N′-bis(2,6-dimethylphenyl)-3,4,9,10-perylenediimide (NI
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Chemical Reviews
Figure 34. Time-resolved fluorescence spectra of (A) no doped, (B)
0.10 mol % coumarin-doped, and (C) 0.36 mol % coumarin-doped
BpPMO. Inset: fluorescence rise and decay curves of the sample in
(C). Reprinted from ref 401. Copyright 2013 American Chemical
Society.
and PDI in Scheme 5 and Figure 35).402 The optical properties
of these complexes could be tuned depending on the
concentration of NI in the composite. At lower concentrations
of NI (D), a blue emission was recorded and assigned to
monomers, while using a higher NI loading, a green emission
Figure 35. Cartoon showing PDI-doped SBANI materials and FRET
from NI to PDI dyes. Reprinted from ref 402. Copyright 2015
American Chemical Society.
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was observed and attributed to aggregate species.402 The
Fö rster radius (R0) was found to depend on sample
concentration, being, respectively, 2.5 and 3.1nm in diluted
and concentrated ones, and the EnT process is less efficient in
the former. Nanosecond time-resolved fluorescence experi-
ments were performed in concentrated NI (D) samples at
different concentrations of PDI (A). In its absence, the sample
exhibits biexponential behavior with time constants of τ1 = 6.6
ns and τ2 = 35.9 ns, assigned to the emission of monomer and
aggregate NI species, respectively.402 However, in the presence
of 9% mol of PDI, the sample displays a triexponential behavior
with time constants, τ1 = 2.2 ns, τ2 = 9.6 ns, and τ3 = 48 ns. The
shortest component reflects the EnT process from NI to the
PDI, while the other time constants are due to the emission of
monomer and aggregate NI species, respectively.402 For these
composites, the emission spectra span the whole visible
spectrum, making them strong candidates for white-emitting
LEDs.
3.3.2.2. Systems with Acceptor Dyes Bound to a
Mesoporous Surface. Another approach to making artificial
D−A antennas is binding the acceptor entity to the outside
surface of the silica-based material. A hybrid photostable energy
D−A mesoporous SBA15 silica system was made in this
manner (Figure 36).377 In this composite, the energy D, Super
Figure 36. (A) Schematic representation of the synthetic route for the
studied hybrid antenna. Digital photographs under UV light of (a)
SY@SBA-15, (b) IRIS3@SBA-15, and (c) IRIS3-SY@SBA-15 in (B)
2-propanol suspensions and (C) powder. Reprinted with permission
from ref 377. Copyright 2012 Wiley-VCH.
Yellow (SY) polymer, is encapsulated in SBA15 pores, while
the A, IRIS3 cyanine dye, is covalently linked to the outside of
the framework (Scheme 5). Time-resolved fluorescence studies
showed that the SY/SBA15 complexes behave differently in the
absence and presence of IRIS3. While that of SY/SBA15 decays
biexponentially (τ1 = 1.1 ns and τ2 = 6.8 ns) with an average
lifetime of 3.5 ns, the fluorescence of IRIS3-(SY/SBA15) is
monoexponential (2.1 ns), indicating that FRET occurs from
the caged SY polymer to the externally linked IRIS3 cyanine
dye.377 The FRET efficiency, R0, and kEnT were calculated using
the emission lifetimes to be 40%, 37 Å, and 1.90 × 108 s−1,
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Chemical Reviews
Figure 37. (A) Structure composition of coumarin/DOC/phyllosilicate hybrids. (B) Cartoon of 7-hydroxy-4-methylcoumarin and DOC molecules
confined to the interlayer of a phyllosilicate. The arrows show the energy transfer from coumarin to adjacent DOC via ultrafast FRET and from
remote coumarin to DOC via radiative transfer. Reprinted from ref 408. Copyright 2010 American Chemical Society.
respectively.377 The high efficiency of EnT in this hybrid system
is due to the large spectral overlap between the D emission and
A absorption. On the other hand, the estimated D−A distance
is consistent with the thickness of the silica wall of SBA15 (33
Å), confirming that the IRIS3 dye is anchored on the external
surface of the material and not inside its pores.377
Similar nanoscale architectures in which R6G was encapsu-
lated in the channels of MCM41 with different amounts of gold
nanoparticles (Au NPs) anchored on the silica surface have
been designed.403 The photoluminescence intensity of the
caged R6G dye is quenched by Au NPs. The quenching
efficiency (76, 64, and 27%) depends on the concentration of
the Au NPs [1:0.05, 1:0.1, and 1:0.2 Au:(R6G/MCM41) ratios,
respectively].403 The fluorescence lifetimes behave similarly,
resulting in average decay times of 1.85, 2.16, and 3.17 ns for
Au:(R6G/MCM41) ratios of 1:0.05, 1:0.1, and 1:0.2,
respectively, while the decay lifetime for the R6G/MCM41
composites without AuNPs is 3.90 ns.403 Therefore, the
decrease in the R6G photoluminescence intensity and the
decay times in the presence of Au NPs confirm the occurrence
of EnT. Its efficiency from the trapped R6G molecules to the
external Au NPs are 52, 44, and 17% for the R6G/MCM41
composites that contain 0.05, 0.1, and 0.2 relative amounts of
R6G, respectively.403 As the number of Au nanoparticles
relative to that of the R6G/MCM41 composites increases, the
narrowing of the EnT channel becomes more evident. This
decrease in the EnT efficiency is due to the formation of Au
NPs aggregates induced by a self-assembly on the MCM41.
This aggregation produces a new plasmonic band in the long-
wavelength region of the absorption spectrum, consequently
reducing the required spectral overlap.403 The distances (r)
between the D and the A (r = 79, 85, and 119 Å for 1:0.05,
1:0.1, and 1:0.2 Au:(R6G/MCM41) ratios, respectively) were
estimated by the surface energy transfer (SET) method.403 This
way is useful in calculating long EnT distances, which is not
possible with the FRET process because its upper limit distance
is 80 Å.403 Finally, anisotropy decay experiments revealed that
R6G molecules are aligned into the channels of the mesoporous
silica, and that the EnT process is unidirectional.403 Therefore,
supramolecular organization inside and outside the channels
leads to more efficient light harvesting systems.
Similar studies were carried out using C480 (Scheme 4),
confined in Y-zeolite functionalized with Au NPs.404 The
fluorescence anisotropy decay of C480 increased from 100 ps in
bulk water to 770 ps in zeolite Y due to the restricted rotation
of the dye imposed by the confinement of the zeolite cavity.
C480 can undergo easy twisting motion, leading to faster
emission depolarization.306,311 Such a phenomenon has been
explored in coumarin 30 (C30, Scheme 5), using chemical
(CDs) and biological (HSA protein) cavities.405 The average
fluorescence lifetime of coumarin 480 was 5.7 ns in zeolite
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without Au NPs but 1.7 ns in the Au-zeolite composites. The
presence of Au NPs also was accompanied by a decrease in the
fluorescence quantum yield. Estimated efficiency of EnT from
the dye to the Au NPs is 70%. Using the SET method, the
distance between C480 and Au NPs attached to zeolites was
estimated to be approximately 70 Å.
3.3.3. Donor/Acceptor Concentration Effects on
Energy Transfer. The role of the relative concentrations of
energy D and A partners is also an important factor to consider
in EnT systems. Homo EnT (A and D have the same molecular
structure) is described in the section on aggregates. Here, we
will focus on hetero transfer (A and D have different molecular
structures). In a system containing fluorescein (D) and RhB
(A) in silica materials (Scheme 5), two types of dye-silica
nanoconjugates have been designed and examined: one based
on silica nanoshells (SNS-dye) and another on silica nano-
particles (SNP-dye).406,407 In both nanosystems, the concen-
tration of donor molecules affects the FRET efficiency and
dynamics. While the amount of acceptors was kept constant,
the D:A concentrations ratio changed from 0.5 to 3 in SNS-dye
and from 0.5 to 4 in SNP-dye systems.406 Femtosecond
fluorescence experiments showed that when the SNS-dye is
excited at 520 nm, a residual D emission was observed at all
values of the [D]:[A] ratio. However, when the SNP-dye was
excited, the D emission was quenched systematically from [D]:
[A] = 0.5:1 to 2:1, leaving only residual emission in the case
when [D]:[A] = 4:1. These results indicate that EnT in SNP-
dye is more efficient than in SNS-dye.406 When SNS- and SNP-
dyes are excited at 630 nm (A absorption region), a long
lifetime component from the acceptor was observed, reflecting
a less efficient EnT process than that at 520 nm. Moreover,
when the mixtures were excited at the A region, differences
between the SNS-dye and SNP-dye emission transients were
recorded. For the case of SNS-dye, a risetime of 500 fs in the
emission signal of [D]:[A] = 0.5:1 to 2:1 confirmed the
occurrence of FRET, while for [D]:[A] = 3:1 and all [D]:[A]
ratios with SNP-dye, no risetime was observed.406 The absence
of the rise time signal is due to an ultrafast and efficient FRET
in the SNP-dye system that is not happening in the SNS-dye
one. For example, the FRET efficiency in SNS-dye and SNP-
dye with a [D]:[A] = 2:1 ratio, was 91 and 97%, respectively.
The difference was explained as a result of the different
methods of synthesis of both nanoconjugates.406 For the case of
SNP-dye, the synthesis leads to dye-rich core formation which
results in dye molecules with a high proximity, generating
FRET in a more efficient way than in the SNS systems. On the
other hand, an increase in the D concentration decreases the
FRET efficiency of both complexes (60 and 66% for [D]:[A] =
3:1 in SNS and [D]:[A] = 4:1 in SNP systems) due to
competitive self-quenching of D molecules.406,407 Thus, the
union of the D and A molecules with these nanoconjugate
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Chemical Reviews
systems forms FRET nanostructures that are highly efficient,
but an optimum concentration of both partners is desired to
achieve a maximum EnT yield.
Another system where efficient FRET depends on the
molecular concentration is formed by coumarin (7-hydroxy-4-
methylcoumarin, Scheme 5) acting as D and cyanine (3,3′-
diethyloxacarbocyanine, DOC, Scheme 5) acting as A confined
in the interlayers of aluminum silicate nanofilms (Figure
37).408,409 In this case, the A concentration is changed relatively
to that of D by using different [DOC]/[host hybrid] ratios (x =
0.1, 1.0, and 10 mmol/100 g). The fluorescence spectra change
with the DOC concentration. At x = 0.1, the D and A
molecules have similar emission intensities, while at x = 10, the
D emission decreases.408 Time-resolved photoluminescence
experiments showed the existence of two different EnT
processes: an ultrafast FRET (in less than 5 ps) from coumarin
to an adjacent DOC, and a slower process (2.2 ns), which is a
radiative transfer from distant D and A entities (Figure
37).408,409
These results reflect the inhomogeneity in the distribution of
the dye molecules in the composite. The fast FRET originates
from short-range interactions between D and A molecules,
which are more common at higher A concentrations, while the
slow process is associated with the emission and reabsorption
of photons (radiative transfer).408 To calculate the FRET
parameters, two- and three-dimensional (2D, 3D) cases were
considered. For the 2D case, R0 is considered to be longer than
the layer-to-layer thickness, while for the 3D one, the opposite
situation is assumed because R0 of the D−A pair is in the range
of 2−9 nm.408,410 Figure 38 shows a comparison between the
2D and 3D models in addition to the experimental decays. For
the 2D scenario, rapid components that decay proportionally to
Figure 38. (A and B) Comparison of the observed donor (7-hydroxy-
4-methylcoumarin) emission decays at different acceptor concen-
trations (c) and simulations for the 2D (C and D) and the 3D (E and
F) cases. Reprinted from ref 408. Copyright 2010 American Chemical
Society.
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t1/3 (t is time) are superimposed on the D’s radiative decay. The
contributions of these components in the emission signal
become larger with increasing A content. However, for the 3D
model, the component decays as t1/2, and this contribution is
smaller than that observed for the 2D one.408 For this
composite, the association of A and D partners originates from
an intercalation process in the synthesis that incorporates the A
molecules by diffusion. During this intercalation, the molecular
flow was limited to 2D motion inside the layer. As a
consequence, the 2D model, used to determinate the FRET
parameters, is more accurate than the 3D one.408 The obtained
FRET efficiency depends on the A concentration, which is 40,
70, and 90% for x = 0.1, 1.0, and 10, respectively. An increase in
A concentration favors their proximity with D, which are
confined in the interlayer of the silica, enhancing the efficiency
of the 2D energy-transfer process (Figure 38). It has been
proposed that a larger amount of A and D can enable other
competitive processes such as self-quenching, dye aggregation,
Homo-energy transfer (Homo-EnT), and collective excitation
effects due to exciton formation.408
3.3.4. Energy Transfer in Silica-Coated Quantum Dots
and Metal Nanoparticles. Silica overlayers have been
frequently used as protective or insulating materials deposited
on various nanostructures, especially semiconducting quantum
dots (QDs) or metal nanoparticles. QDs possess remarkable
absorption and emission bands that are highly tunable upon
shifting their diameters below the Bohr exciton radius, typically
in the single nanometer range.21,411 At the same time, various
additional recombination processes occur that are not observed
in the bulk crystals, with possible modifications helped by the
presence of the silica coating. Metal (especially gold and silver)
nanostructures exhibit surface plasmonic resonance, which can
greatly enhance both the absorption and emission properties of
neighboring chromophores, with potential applications in, for
example, solar cells, LEDs and bioimaging.21,412,413 However,
overly close contact between the chromophore and metal
particle might result in unwanted efficiency quenching, and
therefore, the silica layer can act as a spatial separator.
A few such studies also investigated the photoinduced
dynamics occurring on the ultrafast time scale. CdSe nano-
crystals were coated with silica shells and coupled to Au NPs.414
The average fluorescence lifetime of the silica-coated nano-
crystals (emission spectrum peaking at 600 nm) not interacting
with Au particles was 18.4 ns. This lifetime decreased to 12.5
and 2.7 ns upon interaction with self-assembled films of Au on
different substrates. In the case of the shortest decay (2.7 ns),
the Au plasmonic band was more intense and better suited to
the emission band of CdSe QDs. At the same time, the CdSe
fluorescence intensity increased by a factor of 3 upon coupling
to Au NPs. This result was explained by a significant
enhancement of the excitation rate due to plasmonic resonance
induced by Au particles. Moreover, a strong blinking
suppression was also observed for the CdSe-Au system, with
an increase in the on-state fraction from 60% to more than
90%.414
The fluorescence enhancement of CdTe QDs interacting
with Au NPs was studied with different silica coating layer
thicknesses.415 The optimum SiO2 thickness was 4 nm, which
resulted in approximately 10 times more intense composites
fluorescence than that of bare CdTe QDs (Figure 39). The
photoluminescence time was decreased from 13 ns for the bare
material to 2.8 ns for the optimum gold-silica composite, which
confirmed an increase in the radiative decay rate of photo-
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Figure 39. (A) Photoluminescence spectra and (B) emission intensity enhancement factor F for Au-SiO2 core−shell composites (ASC) of different
SiO2 thickness. (C) Emission decays of the bare CdTe and interacting with ASC of 4 nm. The inset shows the value of decay time constants.
Reprinted with permission from ref 415. Copyright 2013 The Optical Society.

Figure 40. (A) Illustration of the synthesis procedure of SiO2-coated CdTe quantum dots. (B) Biexciton Auger recombination lifetime vs
photoluminescence peak wavelength for CdTe cores (red ▲) and SiO2-coated CdTe quantum dots (blue squares); different peak positions
correspond to different size of CdS clusters. Reprinted with permission from ref 419. Copyright 2011 Royal Society of Chemistry.

excited fluorophores, attributed to the surface plasmonic
resonance effect, due to an increase in the recombination rate
constant of electrons and holes. The enhancement factor
decreased when the SiO2 thickness was above 4 nm. When the
CdTe QDs were too close to Au NPs (silica shell of 1 nm), the
radiative decay rate decreases, while the nonradiative decay rate
was increased, resulting in emission quenching. Similar
observations were reported for Au nanorods coated with a
silica layer and CdTe QDs attached to the silica surface.416 The
luminescence lifetime of CdTe decreases from 37 to 23 ns due
to the increased radiative rate in CdTe upon interaction with
the Au nanorods, while the isolation of the silica layer prevents
their quenching effect.
Composites of silica-coated gold nanorods and chlorine e6
(Ce6, Scheme 5) photosensitizers were studied, motivated by
the search for new drug release methods.417 The mesoporous
silica shell contained amidogen so that the Ce6 molecules were
easily conjugated. The fluorescence lifetime of Ce6 was found
to change drastically from 0.9 ns when attached to the gold-
silica complex to 6 ns after its release. The release could be
controlled by the power of the near-infrared (780 nm)
continuous laser irradiation. Due to the strong absorption of
Au nanorods at the surface plasmonic resonance band, the 780
nm laser beam could heat the system to release Ce6. The silica
coating results in an enhanced and red-shifted surface
plasmonic resonance band.
Au-SiO2 core−shell NPs were studied in a dye-sensitized
solar cell system by an ultrafast transient absorption
technique.418 A plasmon-enhanced light absorption of Z907
ruthenium dye was observed, accompanied by an increased
photocurrent in the cells. However, the studies did not give a
direct conclusion on whether there was discrete EnT from the
plasmon mode to the excited dye state or if there was a direct
near field coupling. For the sample with the core−shell metal−
AK
silica NPs, the intensity of the dye photobleaching band was
greatly increased, but it suffered from a strong quenching with a
5 ps time constant. It was concluded that the plasmon-
enhanced photocurrent generation could be observed only if
the excited dye undergo ET into the titania in the first tens of
femtoseconds. After this time window, resonant plasmons were
very likely to lose their coherence.418
The photoluminescence intensity of QDs is often decreased
due to the presence of Auger recombination. It is the primary
exciton loss mechanism in colloidal nanocrystals not observed
in bulk crystals. A way to reduce this effect was proposed for
CdTe QDs coated with a silica layer.419 This shell contained
small 1 nm CdS-like clusters, which were formed due to the
dispersion of Cd2+ and thioglycolic acid in the silica shell
(Figure 40A). The biexciton Auger recombination lifetime was
5.4 ps for the bare CdTe QDs, while in the hybrid silica shell
structure, it increased to 19.2 ps. Moreover, the recombination
lifetime increased with the size of the CdS-like clusters (Figure
40B). Nonradiative Auger recombination was also investigated
for giant CdSe/CdS QDs with additional silica coating.420 The
observed splitting of exciton states was explained by the
modified charging environment due to the presence of the silica
shell. At low excitation fluences, the measured lifetimes were
longer than 20 ns, and the charged exciton states showed
strongly suppressed Auger recombination rates, resulting in
photoluminescence quantum yields close to 50%. However, at
higher excitation fluences, the consecutive emergence of lower
efficiency states was observed, indicative of higher-order
excitons.
Much longer emission lifetimes (microsecond regime) were
recorded for dense silicon nanocrystal ensembles fabricated by
ion implantation into a SiO2 layer.421 The photoluminescence
quantum yield was measured as a function of silica thickness,
reaching values as high as 60% at low excitation power. At high
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Scheme 6. Molecular Structures of the Compounds Interacting with SBMs and Discussed in the Aggregates Formation Section
(Section 3.4)
fluences, the quantum efficiency was reduced, and internanoc-
rystal nonradiative decay processes were proposed as a possible
mechanism responsible for this decrease, in addition to
biexciton formation followed by Auger recombination.
3.4. Homo-Energy Transfer and Aggregates Formation
EnT between the same dye molecules (Homo-EnT) is a special
case.369,373,422,423 It is strongly related to the formation of
molecular aggregates, which are favored in the confining space
provided by the nanochannels of mesoporous materials and
zeolites. Thus, these two related phenomena (aggregation and
homo-EnT) will be reviewed simultaneously.
Many fluorescent dyes with planar molecular structures
consisting of three or more fused aromatic rings, such as
rhodamines,424−426 pyronines,72,390,394,427 thionines,428,429 and
oxazines,430−432 tend to aggregate at relatively low concen-
trations. This molecular packing can result in formation of H-
(face-to-face) and J-aggregates (face-to-edge), which have
different spectroscopic and dynamical behaviors. Classical
exciton theory predicts a splitting of the monomer excited
state level into higher and lower exciton bands of the
aggregates. But only one transition is allowed to give an
absorption band, which depends on the type of aggregates. H-
aggregates are characterized by absorption bands at high
energies (S0→ S2 transitions), and the S0→ S1 transition is not
AL
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allowed.433−435 In contrast, J-aggregates exhibit absorption
bands at lower energies (S0→ S1 transitions).434,436 H- and J-
aggregates have different dynamics than their monomer species.
Generally, for the aggregates, the emission lifetimes are shorter
than that of the monomers because of efficient deactivation
processes (e.g., EnT) that are caused by the molecular packing
of the monomers.433−436 Furthermore, for H-aggregates, this
emission quenching is high as the probability of radiative
transition from its S2 state is very low.434,437 The theory and
experimental supports are well-documented and re-
viewed.422,433−435,437−441 When the monomers are being
encapsulated within the nanomaterial pores/cavities, aggregates
formation can be either favored or inhibited, depending on the
molecular structure of the guest and the type of silica-based
material used.
Hemicyanine dyes (Scheme 6) that were encapsulated in
nanosized pores of zeolites show this kind of behavior.442
Steady-state experiments indicated high fluorescence quenching
as the concentration of the dye increased and the
intermolecular distance shortened (from 12.6 to 2.1 nm).442
The emission quenching was explained in terms of an
intermolecular dipole−dipole interaction (FRET) between
the dye molecules (i.e., one excited hemicyanine molecule
transfers its electronic energy to a hemicyanine in the S0 state).
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Figure 41. (A) View along the straight channels of the MAPO structures and (B) fluorescence images of PY dye in different MgAPO structures:
MgAPO-5, PY/AFI-H (left); MgAPO-36, sample PY/ATS-H (center); and MgAPO-11, PY/AEL-H (right). Reprinted with permission from ref 390.
Copyright 2013 Wiley-VCH.
Analysis of the time-resolved data showed that efficient EnT
occurs when the intermolecular distance is longer than 5 nm
(R0 = 2.2 nm). The emission decays were fit with a
biexponential function. The shorter average time constant
(800 ps) was assigned to the lifetime of guest molecules near
each other, and a 2.2 ns time constant was attributed to
monomers that were not interacting with others.442 Another
example of a molecule that forms caged aggregates is Py, a
xanthene-derivative dye (Scheme 2). Different loadings of Py
encapsulated in zeolite L have been investigated.394 At highly
diluted conditions (0.6% loading), the composite exhibits
similar behavior to that observed for the free Py in solution,
indicating that the caged Py molecules are present as isolated
monomers.394 However, at higher concentrations (20%
loading), the caged Py molecules form J-aggregates, generating
additional red-shifted transitions and shortening the fluores-
cence lifetimes. At this loading, a biexponential fluorescence
was observed, with lifetimes of 0.7 and 2.9 ns, assigned to J-
aggregates and monomers inside the zeolite, respectively.394
Similar observations have been reported for perylene dyes
(N,N′-bis(2,6-dimethylphenyl)-3,4,9,10-perylenetetracarboxylic
diimide (DXP), N,N′-bis(3,5-dimethylphenyl)-3,4,9,10-peryle-
netetracarboxylic diimide (PR149), and N,N′-bis(1-hexylhep-
tyl)-3,4,9,10-perylenetetracarboxylic diimide (HPDI), Scheme
6) interacting with zeolite L.395 Interestingly, for these
composites, the presence of substituents on the pyrene
structure can inhibit or favor the molecular packing.395 DXP
exhibits aggregation, while PR149 and HPDI do not show it.
Another factor that obviously influences the formation of
aggregates is the concentration of the dye inside the zeolite
cavities. This controllable factor provided to observe interesting
behavior of DXP/zeolite L composites, whose spectroscopic
properties strongly depend on the loading. Under diluted dye
suspensions, monomers emission is mainly recorded (with a
lifetime of 3.8 ns), while at high dye loadings, a significantly
shorter lifetime (from 1.7 to 0.7 ns), assigned to J-aggregates,
was reported.395 In contrast, the voluminous groups of PR149
and HPDI prevent these dyes from packing at the sufficiently
short center-to-center distance that is needed for strong
coupling.395
Aggregates formation in SBMs was also controlled by
modulating the host properties. This has been demonstrated
by encapsulating Py in aluminophosphate zeotype (APO)
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materials with a variety of structure types such as AFI, ATS, and
AEL.390,427 The differences among these 1D structures mainly
reside in their pore dimensions, which are 7.3 × 7.3 Å2 for AFI-
(MgAPO-5), 6.7 × 7.5 Å2 for ATS- (MgAPO-36), and 4 × 6.5
Å2 for AEL-structures (MgAPO-11) (Figure 41A).390 Within
MgAPO-5 (AFI structure), H-aggregates are formed, and their
fluorescence is quenched strongly decreasing the quantum
yield: ϕ (%) = 0.4 versus 22 for PY in solutions (Figure
41B).390,427 The larger pore dimensions of the AFI structure
allow the population of unrestricted face-to-face (H-aggregates)
conformations, even at low concentrations.390,427 Their
population can be reduced by decreasing the Py concentration
and by increasing the Mg content.427 Inhibiting the formation
of this type of aggregates, by decreasing the pore size of the
host, was reached using MgAPO-36 materials.390 In this case,
the MgAPO-36 structure allows face-to-tail interactions and
thus J-aggregate formation of Py (Figure 41B).
Interestingly, Py monomers emit green (560 nm, 3 ns) light,
while J-aggregates in the composites emit red (660 nm, 1
ns).390 The interaction of PY with MgAPO-11 materials, whose
pore width (6.5 Å) is similar to the Py cross dimensions (6.8 Å,
measured perpendicular to its main axis), was investigated.
Only the caged monomer was observed, and it emits with a
longer lifetime than Py in solutions (3 vs 2 ns, respectively),
reflecting the rigidity that the matrix imposes on the monomer
movement, limiting then its nonradiative processes (Figure
41B).390 Similar behavior was reported for rhodamine
dyes.391,392,424−426,443−451 When R6G (Scheme 5) intercalates
into solid thin films of laponite (Lap) clay, it tends to self-
aggregate, resulting in trapped H- and J-aggregates.426,447
Under very diluted conditions, only the R6G monomer was
observed, with an absorption band centered at 528 nm and an
emission one at 548 nm.426,447 The average lifetime of the
monomer is 4.2 ns, which is slightly longer than in ethanol
solution (3.95 ns) and reflects the weak confinement effect on
the emission decays of the inorganic nanostructured materi-
al.446,447 When R6G concentration increases, H- and J-
aggregates are formed.426,447 Their gradual formation is
evidenced by the quenching of the fluorescence signal and
progressive decrease in the average emission lifetime from 4.2
ns (average lifetime in diluted solutions) to 0.45 ns (average
lifetime in concentrated solutions).447 These results show that
the ratio of H- to J-aggregates increases with the increased dye
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Chemical Reviews
Figure 42. (A) Schematic representation of various sites at clay mineral surface, such as (a) external, (b) internal or interlayer, and (c) particle edges.
(B) Fluorescence decay curves recorded at 595 nm after excitation at 410 nm of rhodamine 3B/montmorillonites dispersions. Reprinted from ref
391. Copyright 2007 American Chemical Society.
loading.447 However, different behavior was observed in
mesostructured 2d-hexagonal silica films.424 Steady-state experi-
ments revealed that at low dye concentrations, H-aggregates
preferably form, while at high concentrations, J-aggregates are
favored due to the presence of the templating cylindrical
copolymer micelles that are highly organized into a 2D-
hexagonal (p6mm) symmetry within the mesopores.424 The
aggregation of R6G has also been investigated in the presence
of organic−inorganic silica hybrids that were prepared using a
sol−gel synthesis (bulk sample) and by spin-coating methods
(thick film samples with a thickness ∼2 μm).451 For thick film
samples, irrespective of the dye concentration, no aggregates
were observed. However, in the bulk samples, J-type aggregates
were formed, along with the corresponding decrease in the
fluorescence lifetimes, due to enhanced nonradiative tran-
sitions.451 Comparable behavior was reported when a similar
dye, rhodamine 3B (Rh3B, Scheme 6), was adsorbed on the
surface of montmorillonite layers (Figure 42A).391,392,445 The
presence of diethyl substituents at the N atoms of Rh3B and of
Li+ cations in the montmorillonite structure prevents the
formation of H-aggregates and favors J-ones.391,445,452,391 The
high heterogeneity of the system results in four emission
lifetimes (∼40 ps and ∼ 250 ps and ∼ 1 ns and ∼2 ns) of the
excited composites. When the system is heated, the population
of J-aggregates increases, evidenced by the value of the average
fluorescence lifetime, which changes from 710 ps at 0 °C to 460
ps at 130 °C (Figure 42B). The average lifetime of Rh3B in the
hybrid complexes is shorter than that in water (1.53 ns), which
indicates that an efficient quenching process occurs when Rh3B
interacts with these materials.391 The decrease in lifetime values
is explained in terms of aggregates formation that enables new
deactivation processes such as internal conversion and homo
EnT reactions.
Photochromic aromatic Schiff bases with an IHB, belonging
to the family of salicylideneanilines (SAs), also show a tendency
to form aggregates upon encapsulation.263−267 HBA-4NP, a
derivative of SA, forms H- and J-aggregates when it is trapped
in faujasite zeolites, MCM41 and SBA15 materials (Scheme
3).264−267 In a pure dichloromethane solution, no aggregation
was observed. The emission spectrum exhibits an intensity
maximum at 580 nm (Stokes shift ∼11,400 cm−1) due to the
formation of the K* tautomer that is created after an ultrafast
ESIPT reaction (<50 fs, see section 3.1) in the E* structure.
The K* species has a fluorescence lifetime of 14 ps, which is
very short because a twisting motion enhances the radiationless
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Review
decay.266 When encapsulated in micro- and mesoporous
materials (NaX, NaY, MCM41, AlMCM41, and SBA15),
HBA-4NP forms H- and J-aggregates. The absorption spectrum
of caged HBA-4NP has bands at 325, 370, and 410 nm,
assigned to the absorption of the H-aggregates, monomers, and
J-aggregates, respectively. The emission spectrum exhibits a
broad band with three intensity maxima (460, 480, and 530
nm), which are due to the emission of the K* forms of the
monomer and J- and H-aggregates, respectively.264,265 The
changes reflect the presence of these new species, whose
formation is related to the size and composition of the host. For
example, when HBA-4NP is encapsulated in zeolites, different
loading yields were observed, depending on the host (90% for
NaY while 20% for NaX).264 The characteristics of the space
available within the host determines the loading yield; thus, in
NaY, which has fewer sodium cations and aluminum atoms in
its framework, there is a stronger tendency to form dye
aggregates than in NaX.264 When HBA-4NP is trapped in
MCM41 and AlMCM41, whose identical pore sizes are wider
than that of the faujasite zeolites (2.5 vs 1 nm, respectively),
high loading yields (85 and 95% for MCM41 and AlMCM41,
respectively) and larger amounts of aggregates were
reported.265 However, there is less aggregates formation in
SBA15, a host with a wider pore size (∼6 nm), due to a weak
loading yield (40%).265 In all the studied complexes, the ESIPT
reaction is very fast (<50 fs), leading to K* structures of the
monomer and aggregates. The fluorescence lifetime of the
caged K* monomer is remarkably longer in silica-based
materials (∼6 ns in NaX and NaY and ∼3 ns in MCM41,
AlMCM41, and SBA15) than in dichloromethane solution (14
ps).264,265 These changes in lifetime reflect the large degree of
restricted movement that is enforced by these hosts. The
lifetimes of the trapped H- and J-aggregates are 100 ps and 1 ns,
respectively, and they become shorter with an increase in the
guest concentration.264 The photobehavior reflects the
presence of monomers and aggregates in the composites; the
formation and stability of the H- and J-aggregates depend on
the properties of the material. For example, SBA15 composites
have the lowest population of aggregates due to their low
Brunauer−Emmett−Teller (BET) surface area (780 m2/g vs
825 m2/g for NaX, 1430 m2/g for NaY and 1000 m2/g for
MCM41/AlMCM41) and their surface roughness, which has
fewer OH groups.265 In contrast, when MCM41 and
AlMCM41 composites with the same BET surface area and
pore sizes are compared, the latter hosts more J-aggregates
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Chemical Reviews Review

Figure 43. Representative emission transients of HBA-4NP in dichloromethane solutions and interacting with NaY cavities prepared from diluted (2
× 10−6 M) and concentrated (2 × 10−3 M) parent solutions. The insets show trapped monomers, H- and J-aggregates of HBA-4NP in the zeolite.
Reprinted with permission from ref 266. Copyright 2017 Elsevier B.V.

Figure 44. Cartoon showing the NR molecular structures (monomers, H- and J-aggregates) interacting with (A) X-MCM41 and (B) faujasite
zeolites. (A) Reprinted from ref 227. Copyright 2015 American Chemical Society. (B) Reprinted from ref 457. Copyright 2018 Elsevier B.V.

because of Al doping, which results in charge defects, increase
in the acidity of the pores, and thus the interaction between the
guest molecules and the framework. The host−guest and
guest−guest interactions also play an important role in the
ultrafast (fs-scale) behavior of these complexes. In dichloro-
methane solutions, the fluorescence of HBA-4NP exhibits two
ultrafast components that are assigned to IVR (100 fs) and a
combination of VR/cooling and twisting motion (1.2 ps).266
These ultrafast processes slow down when HBA-4NP is
dissolved in a highly viscous medium (180 fs and 2.5 ps,
respectively, in triacetin solutions), reflecting the internal
molecular motion in excited K*. This situation is reminiscent
of that of trapped HBA-4NP, as the confinement effect
produced by the host, on aggregates formation, specific and
nonspecific interactions with the host framework, leading to
slower dynamics (Figure 43).266,267 Thus, in SBA15 complexes,
the IVR and VR/cooling processes have time constants (200 fs
and 2 ps) that are similar to those obtained in solutions, as the
caged monomer species is predominant, and there is less
restriction to movement.267 However, within NaX, NaY,
MCM41, and AlMCM41 materials, the values of these
components increase to 300−450 fs and ∼3−4.5 ps,
respectively, because of guest−guest interactions in the
aggregates. The dynamics in the MCM41 and AlMCM41
composites, materials with larger pore sizes and more OH
groups on the framework, are slightly slower (370 fs and 3.4 ps
AO
for MCM41 and 450 fs and 4.5 ps for AlMCM41) than the
dynamics in materials with smaller pores such as NaX and NaY
(300 fs and 3 ps).266,267
NR also forms H- and J-aggregates in the presence of
nanostructured host materials (Scheme 4). Its behavior in
heterogeneous and organized media such as polymeric
nanoparticles,453,454 micelles,318,455 cyclodextrins,317 zeo-
lites,293,456,457 and proteins294 has been widely studied. It
forms aggregates in silica materials such as silica sol gels,
laponite nanoclays, and MCM41 as a result of interactions with
the host matrix.226,227,458−461 In solution, it does not exhibit any
signs of aggregation.227,295,462,463 Time-resolved emission
studies show that monoexponential decays (2.80 ns in
methanol, 3.65 ns in ethanol, and 4.4 ns in dichloromethane)
reflect the existence of only the monomer species.227,462 When
NR interacts with laponite materials, it forms aggregates of
mostly the H-type.461 NR-laponite hybrid materials loaded with
different amounts of the dye exhibit an unstructured broad
absorption band that has two intensity maxima (550 and 600
nm) assigned to H-aggregates and the monomer species,
respectively.461 The decrease in the fluorescence quantum yield
from 34 to 14% in the composites of 0.06 and 0.5 NR
molecules per disk of the host material also demonstrates the
presence of these aggregates that are not highly emissive.461
The introduction of the cationic surfactant CTAB suppresses
the formation of H-aggregates in these hybrid systems and thus
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increases the fluorescence quantum yield in the laponite
systems.461 In a series of MCM41 that was doped with different
metals (M = Al, Ga, Ti, and Zr), it was found that the
composites fluorescence decay is multiexponential, in contrast
with the monoexponential behavior in pure solvent.227 When
NR interacts with regular MCM41, three lifetimes appear in the
fluorescence decay (τ1 = 0.3 ns, τ2 = 0.9 ns, and τ3 = 2.5 ns).
The longest time was attributed to the NR monomers that were
attached to the surface of the host, while τ1 and τ2 were
assigned to H- and J-aggregates, respectively, with the largest
contribution arising from the J-aggregates.227 A significant
shortening in the fluorescence lifetimes was observed upon
increasing the dye loading, supporting the explanation that the
molecular packing of NR within the MCM41 nanopores leads
to the formation of H- and J-aggregates (Figure 44).
The specific and nonspecific interactions of NR with metal-
doped AlMCM41 and GaMCM41 materials only slightly affect
the fluorescence lifetimes and contributions of the NR species
relatively to those in the NR/MCM41 system.227 This result
was explained by the low amount of Al and Ga atoms in metal-
doped MCM41 (3% in AlMCM41 and 3.7% in GaMCM41).
However, the interaction of NR with TiMCM41 and
ZrMCM41 results in a decrease in the fluorescence lifetimes
of the monomers and H- and J-aggregates when compared with
the behavior of NR/MCM41.293 The strong quenching
indicates the opening of a new decay channel that leads to
faster decays of NR molecules when interacting with these
hosts containing transition metals (Ti and Zr). The interactions
in these systems enable electron injection (EI, see section 3.2)
into trap states that are formed by the d-orbitals of the host
metal atoms (Lewis acidity).461 Furthermore, in a study that
used cometal-doped MCM41 materials (Ti-AlMCM41) with
varied Al and Ti contents, the H- and J-aggregate contributions
were related to the content of Brønsted (Al doping) and Lewis
(Ti doping) acidic sites in the silica framework.226 An increase
in the Ti content induces a substantial increase in J-aggregates
population and a shortening in the NR emission decays via ET
to the titania sites.226 In contrast, the formation of J-aggregates
is a result of localized and specific interactions between NR and
Ti-atoms, reflecting the importance of the physicochemical
properties of metal-doped SBMs for the generation and
stabilization of these species. Composites of NR interacting
with faujasite (NaY)-type zeolites having different Na/Al ratios
and charge balancing metals (Li+, Mg2+, and Cs+) in
dichloromethane suspensions have been studied using steady-
state and fs−ps time-resolved spectroscopy.457 The results
show formation of different populations, reflected in H- and J-
aggregates, monomers, and surface adsorbed species (Figure
44B). The Na/Al ratio and the nature of the doping metal ion
affect the relative contribution of each population. The
bathochromic shift of both diffuse transmittance and emission
spectra suggests strong interaction of the dye with Brønsted
and Lewis sites of the zeolites. The femtoseconds fluorescence
transients show an ultrafast formation (∼200 fs) of a CS in NR
followed by a vibrational cooling (1−2 ps). The fluorescence
lifetimes of the composites range from ∼100 ps to ∼2 ns, which
decease at high Na/Al ratios. This behavior is explained in
terms of H-bond formation between NR molecules and the
zeolite framework. Interestingly, the emission lifetimes change
with the metal ion exchanged zeolites, due to the variation in
the properties (size and polarization ability) of the exchange
cation.457 Although the steady-state spectral properties of NR
interacting with the zeolites and MCM41 materials are
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comparable, several differences could be detected. First, the
molecular packing is more efficient in the zeolite nanocages
despite their reduced dimensions (pore/cavity diameters of 35
and ∼13 Å for the mesoporous materials and the zeolites,
respectively). This is reflected in loading efficiencies higher for
the zeolites (∼2.5 × 1018 NR molecules/g zeolite) than those
for the mesoporous materials (∼2.0 × 1018 NR molecules/g
MCM41) under similar experimental conditions. These
differences are due to electrostatic interactions between the
encapsulated NR molecules, the Na+ cations, and the
aluminosilicate framework of the zeolite cavity, which facilitate
molecular trapping.266 While the populations of the caged
monomers and H-aggregates are similar, the one of J-aggregates
is higher within the MCM41 mesoporous materials due to the
higher surface acidity of these hosts, whose SiOH groups
enhance H-bonding interactions with the guest molecules.227
The increased rates of both the fast and ultrafast dynamics for
the excited NR/zeolite complexes compared to those in the
NR/XMCM41 ones reflect stronger host−guest interactions in
the former composites. This effect is more pronounced for the
H-aggregates but is also observed in the case of the J-
aggregates, as well as for the ICT and VC processes. Within the
zeolite cavities, the spatial restriction strengthens the host−
guest and guest−guest specific and nonspecific interactions, and
as a result, the emission lifetimes of the involved species are
shortened, while the ICT process occurs more efficiently.
Furthermore, the restricted motion also increases the vibronic
coupling between the S1 and S0 states, thus enhancing the
nonradiative deactivation pathways.464
In this section, we have shown how the encapsulation of
energy D and A molecules in SBMs enhances their stability,
giving rise to more efficient FRET. The SBMs can act as spatial
separator between D and A molecules, preventing aggregation
and quenching processes, and as protective or insulating hosts
especially for semiconducting QDs or metal NPs. An important
aspect to consider in EnT systems is the relative concentration
of energy D and A molecules trapped in the SBMs pore. A high
concentration of the partners allows close contact between
them but also can give rise to a competitive self-quenching
process. Using 2D nanostructures and/or 3D nanoporous
SBMs with larger pore sizes results in predominant formation
of H-aggregates. However, in 3D materials with smaller pore
sizes and less metal doping in their structures, J-aggregates are
the favored species because of the limited free space and the
promotion of specific and nonspecific interactions with the
framework. This kind of interactions determines the possibility
of EnT and are related to the effectiveness of SBMs for the
development of new technological applications.
4. SINGLE MOLECULE
The design of silica-based host materials is challenging and
often presents difficulties in tuning and assessing the number,
distribution, and nature of acid sites. As we commented on in
the previous sections, along with these challenges, the
distribution of the encapsulated guests and the changes in
their reactivity and photophysical properties remain particularly
exigent issues. Single-molecule/single-nanostructure optical
spectroscopy techniques are best suited to address these and
other open questions related to the characterization of hybrid
complexes. The importance of these advanced tools to the field
of materials chemistry in general and to SBMs in particular has
been highlighted by several recent reviews.17,48,465−470 The
application of single-molecule fluorescence methods to study
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Scheme 7. Molecular Structures of the Compounds Interacting with SBMs and Discussed in the Single Molecule Section 4
mass transport in SBMs has been the topic of a number of
reviews focused on studies that pursued deeper insights into
certain defining properties of porous silica, such as the pore
structure, host−guest interactions, and diffusion dynamics.
These reviews provide examples from the literature that
demonstrate how fluorescence microscopy is used for
elucidating important aspects of porous silica materials and
heterogeneous catalysis (e.g., diffusion, reactivity, morphology,
intergrowth, accessibility, and catalyst deactivation).467,469 The
experimental methods covered in these reviews include single-
particle tracking and confocal and wide-field fluorescence
microscopy. Another topic related to the development and
characterization of SBMs in which single-molecule methods are
of fundamental importance is heterogeneous catalysis. Few
reviews in the field of heterogeneous catalysis have demon-
strated the potential of these techniques for studying the
reactivity of catalyst particles.48,465,466,468,470 Furthermore,
optical super-resolution imaging has recently been reviewed
in light of studies on heterogeneous and homogeneous
chemical reactions at the single-molecule level, including
reactions involving zeolites.17 The high spatial resolution of
optical super-resolution imaging and its ability to monitor
dynamic systems can reveal additional detailed information on
single-molecule reaction/adsorption processes and single-
particle catalytic processes, including chemical kinetics and
reaction dynamics; active-site distributions on single-particle
surfaces; and the size-, shape-, and facet-dependent catalytic
activities of individual nanocatalysts. Single-molecule fluores-
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Review
cence spectroscopic methods have been employed to
investigate the microenvironmental acidity distributions in
mesoporous aluminosilicate thin films that serve as models for
solid acid catalysts. In the following, we will only comment on
the recent contributions not discussed in previous re-
views.17,48,465−470
4.1. Single Molecule Reactivity in Silica-Based Materials
((5′ and 6′)-Carboxy-10-(dimethylamino)-3-hydroxyspiro[7H-
benzo[c]xanthene-7,1′(3H)-isobenzofuran]-3′-one, C-SNARF-
1, Scheme 7) was used as an effective probe of the local pH in
low-pH media (i.e., 1 < pH < 5).471 Histograms of the emission
intensity ratios of C-SNARF-1 single molecules were used to
elucidate the acidity distributions in mesoporous aluminosili-
cate films with varying Al2O3 content. The data revealed an
increase in film acidity with increasing Al2O3 content. The
results were interpreted in terms of a downward shift in the pH
of the local environment from pH ∼ 5 (pure silica) to pH ≤ 3
as the Al2O3 content of the film increased from 0% to 30%. The
distributions obtained are broader than expected for homoge-
neous samples, revealing a high degree of heterogeneity in the
acidity properties of the studied films. Single-molecule
fluorescence-based imaging methods were used to study the
catalytic activity of the zeolite ZSM-5 in cracking processes.472
The presence of Brønsted acid sites in the framework of ZSM-5
leads to the formation of fluorescent products, which were
monitored with single-turnover sensitivity and high spatiotem-
poral resolution. To obtain information on the number and
distribution of Brønsted acid sites, and on the catalytic activity
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of ZSM-5 materials, the acid oligomerization of furfuryl alcohol
(FFA) was used as a primary catalytic reaction. FFA forms
highly fluorescent oligomeric carbocations as result of its
interaction with Brønsted acid sites.472,473 The main conclusion
of that work was that the thermal treatment of ZSM-5
composites changes their reactivity: mild steaming at 500 °C
increases the surface reactivity, with local turnover rates up to 4
times higher than those of the parent ZSM-5 crystals, while
severe steaming at 700 °C significantly dealuminates the zeolite
material, leading to turnover rates that are 460 times lower.473
These differences were explained in terms of the aluminum
distribution, as severe steaming leads to the migration of Al-
species to extra-framework sites, blocking the pore accessi-
bility.473 In a more recent report, the acid-catalytic reactivity of
ZSM-5 zeolite was demonstrated using a PT reaction
(oligomerization of styrene derivatives) as a probe.474 The
oligomerization reaction gives rise to dimeric and trimeric
species, which have different photostabilities and are sensitive
to the solvent conditions. For example, when an apolar solvent
(n-heptane) is replaced by a polar one (1-butanol), the zeolite
reactivity decreases by several orders of magnitude due to the
strong chemisorption of 1-butanol onto the Brønsted acid sites.
Furthermore, the study concluded that the presence and
stability of di- and trimeric species are also influenced by local
structural defects in the ZSM-5 framework. While the dimeric
species are located at the surface and in the middle of the
zeolite crystals, the trimeric ones, which tend to form
aggregates, lie predominantly on the outer surface.474 This
report indicates that the accessibility of the Brønsted acid sites
can largely determine the local reaction rates and product
selectivity.
4.2. Single Molecule Diffusion in Silica-Based Materials
Spectroscopic single-molecule tracking (sSMT) was used to
directly visualize the diffusive motions of uncharged, cationic,
and anionic perylene diimide dyes (TPDI, SPDI, and OPDI,
Scheme 7) in 1D nanochannels within flow-aligned meso-
porous silica monoliths incorporating nanometer-sized cylin-
drical pores.475 The monolith pores were filled with Pluronic
F127 surfactant, water, and alcohol. The study reports both
isotropic and anisotropic diffusion for all three dyes. The
charged dyes exhibit predominantly isotropic motions,
suggesting that these molecules readily pass through defects
in the silica pore walls. In contrast, the motions of the
uncharged PDI became more anisotropic as the monolith ages.
The results obtained from flow-aligned F127 gels in the
absence of silica demonstrate that partitioning plays an
important role in limiting the passage of the PDIs between
pores. The fluorescence correlation spectroscopy (FCS) data
confirmed the presence of two populations of diffusing
molecules, attributable to anisotropic and isotropic motions.
All three dyes exhibit mean diffusion coefficients that decrease
with monolith age. On the basis of combining the sSMT and
FCS data, aging-time-dependent chemical changes to the
materials were suggested, which lead to partitioning of the
charged PDI dyes into more polar regions that facilitate their
passage through the pore walls. In contrast, the uncharged PDI
become better confined to the hydrophobic micelle cores with
monolith aging, leading to enhanced 1D diffusion (Figure
45).475
However, this report did not resolve the location of the dye.
Thus, sSMT studies using the polarity-sensitive dye NR
(Scheme 4) have been performed, showing that the majority
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Figure 45. (A) Model for the localization of uncharged (in
hydrophobic core of the F127) and charged (into the hydrophilic
corona region) probe in the F127 surfactant filling the nanometer-
sized cylindrical pores incorporated in mesoporous silica monoliths,
(B) diffusion modes for anisotropic, and (C) apparent isotropic
diffusion. Reprinted from ref 475. Copyright 2015 American Chemical
Society.
of NR molecules are located in nonpolar local environments
with polarities similar to that of n-hexane.476 NR exhibits one-
dimensional diffusion, which is consistent with its confinement
in the cylindrical pores of surfactant-templated mesoporous
silica films. Single-molecule emission polarization measure-
ments have also demonstrated that NR molecules diffuse with
their long axes aligned parallel to the long axis of the pores and
that they are orientationally confined to ∼0.6 nm diameter
pathways within the pores.476 The diffusion coefficient for 1D-
diffusing NR is also shown to be ∼103-fold lower than in bulk
solution. These results were interpreted in terms of NR dyes
being confined in the hydrophobic cores of the micelles.476
4.3. Other Studies
Single-molecule spectroscopy was also used to study the rate of
surface-support degradation at silica surfaces upon exposure to
bases under a variety of deposition conditions.477 The kinetic
analysis of the obtained experimental results has shown the role
of thermal annealing and the addition of blocking layers in
increasing stability, which is derived not from an increase in the
stability of the surface linkage but from a decrease in the rate at
which base molecules approach the surface before irreversible
attack at the silyl ether linkage. Furthermore, it was suggested
that the structural diversity of the silica surface is likely to be the
cause of the observed heterogeneity in the surface-linkage
disruption kinetics.477
In similarity with other nanostructures, SiO2 nanoparticles
can possess luminescent defects in their regular structure. A
photoluminescence study on defect centers in single 11 nm
SiO2 nanoparticles has shown that the photophysical properties
of these luminescent centers are comparable to those of single
dye molecules.478 It was observed that the fluorescence from
these particles exhibits a linear transition dipole and symmetric
emission and excitation spectra. However, these luminescent
defects have presented larger variability from particle to particle
due to variations in the local chemical environment around
each center of each particle.478 In a consecutive single particle
study, the photoactivation of the luminescent centers in SiO2
nanoparticles with sizes between 11 and 166 nm was
demonstrated.479 The work has shown that by exposing a
single SiO2 nanoparticle to UV illumination, it is possible to
create new luminescent centers within these particles. Due to
the much weaker chemical bonds in the SiO2 particles, it is
possible to generate new defects in the nanostructures using
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UV light, which allows for the reactivation of the nanoparticle’s variation in its optical properties was also recorded, as revealed
fluorescence after its photobleaching.479 by steady-state and time-resolved emission techniques.484 The
4.4. Electronic Nanoconfinement study did not report any effect of the confinement of the
nanochannels on the ESIPT reaction (section 3.1) in the E*
As we comented on in the above parts, the encapsulation of
guest molecules in the channels of micro- and mesoporous structure of HBTNH2 to give K* tautomer, probably as it is
hosts may significantly change the electronic properties of the very fast (<100 fs) and it is not expected to be affected.
guest species, which may give rise to variations in optical band However, the component assigned to the excited-state lifetime
gaps and in the excited-state lifetimes of the organic molecules of the twisted K* of HBTNH2 increases from 22 ps in
in these composites. When a tight host/guest fit is observed, acetonitrile to 40−45 ps within MCM41 in support for the
these changes are reflected in variations in basicity and the electronic confinement effect on HBTNH2.484 Experimental
oxidation potential, for example. These apparent variations evidence for the electronic nanoconfinement of HBTNH2 at
cannot be explained only in terms of the influence of the host the single-molecule level has also been reported.210 Time- and
electrostatic fields on the stabilization of polar guests. An spectrally-resolved studies at the single-molecule level have
electronic confinement concept has been proposed based on demonstrated that depending on the way of the guest−host
the idea that the molecular orbitals (MOs) of the guests inside complex preparation, different sites of the host (MCM41) are
the host (zeolite) pores are not extended throughout the space accessed by the guest.210 The averaged emission spectrum of
but instead are limited to within the zeolite walls.480,481 This the single-molecule complexes (HBTNH2/AlMCM41) reveals
confinement effect is stronger as the size of the confined guest a single band centered at 583 nm with a full-width at half-
approaches the zeolite cage dimension, producing an energy
maximum (fwhm) intensity of 64 nm (∼1480 cm−1). The
increase in all MOs, particularly those that are more diffuse.
Theoretical studies have demonstrated that confining organic emission is assigned to a trapped anion (deprotonated phenol
molecules in the pores and cavities of SBMs is sufficient to alter moiety) of the dye. The spectrum is much narrower than the
their electronic properties as a result of changes in the one of K* generated using the undoped MCM41 (∼3250
molecular orbital energies and band gaps.480−482 Results from cm−1) samples (HBTNH2/MCM41 (Figure 46).
the calculations of the electronic properties of confined
benzene, naphthalene, and anthracene have been presented in
support of the electronic confinement effect.482 These
calculations have demonstrated that the HOMO is more
sensitive to confinement than the LUMO, and the overall effect
is a reduction of the band gap of the frontier MOs when the
guest−surface distance is less than ca. 2.5 Å. In that report, the
confining space of the cavities has been modeled using a mica
sheet with a molecule−surface distance in the range of 1.5−4.0
Å. Evidence of confinement has been revealed by semiempirical
calculations, which were interpreted by means of the Hückel
molecular orbitals theory. More recent calculations predicting
redshift of both absorption and emission bands of the dyes
upon encapsulation are commented in section 2.2. An
experimental evidence of electronic confinement was reported
for anthracene encapsulated within zeolites.464 The study has
reported a bathochromic shift of the 0−0 transition from 375
nm in 3-methylbutane to 396 nm in NaY and to 419 nm in
ZSM-5, showing that the smaller the pore size of the zeolite, the
larger the bathochromic shift of the 0−0 transition. The
observed shift along with the shortening in the fluorescence
lifetime (from 4.5 ns for free anthracene to 3.2 ns within NaY
zeolite and <100 ps in mordenite or ZSM-5) have been
correlated with the increase in the HOMO energy and with the
reduction in the HOMO−LUMO band gap. Other studies have
provided additional experimental evidence for the electronic
nanoconfinement effect in MCM41 and zeolite materials. For Figure 46. Single-molecule microscopy results of HBTNH2 covalently
example, significant variations in the photophysical properties bonded to silica nanoparticle and AlMCM41. (A) Emission decays of
of Py molecules incorporated inside zeolite crystals that have HBTNH2 covalently bonded to silica and (B) AlMCM41, along with
similar channel sizes, such as zeolite L and AlPO4−5, were the best nonlinear least-squares monoexponential fits (solid lines). (C)
observed by means of fluorescence polarization.483 The results and (D) are the distribution of the lifetimes from the monoexponential
indicate that the dye molecules’ optical properties are strongly fit to the decays of single-molecule silica and AlMCM41 composites,
respectively. (E) and (F) represent the average emission spectrum of a
affected by the framework structure of the host, especially the
single HBTNH2 covalently bonded to a silica nanoparticle and
specific geometry of the zeolite channels, which induces an AlMCM41 nanochannels, respectively. The dashed line in part (E)
angle dependence of the guest fluorescence behavior. The represents the Gaussian fit to the main contributing band in the
change was explained in terms of the electronic confinement average spectrum of single HBTNH2-silica complexes in the presence
effect. When the ESIPT dye HBTNH2 (Scheme 3) is of the strong base 1,8-diazabicyclo[5.4.0]undec-7-ene. Reprinted with
encapsulated within MCM41 and Al-doped MCM41, a strong permission from ref 210. Copyright 2010 American Chemical Society.

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This difference, along with the narrower lifetime distribution,
is a clear evidence of a stronger confinement of the local
nanoenvironment around the single anion of HBTNH2 in the
AlMCM41 channels. It is suggested that the replacement of Si
atoms with Al ones changes the electronic density distribution
within the framework of MCM41, which in turn affects the
host−guest orbital interaction that the resulting emission
comes from a much narrower density of the states of the
single chromophore. Studying the single-molecule behavior of
DY-630-MI, a hemicyanine dye (Scheme 7), showed that
replacing a few Si4+ ions with Al3+ ones in the regular MCM41
changes the local electrostatic field within the nanotube, which
results in a more selective orientation of the DY-630-MI
molecules.485 Comparing the distribution of the polarization
(P) values for DY-630-MI/AlMCM41 with those for the free
molecule and the DY-630-MI/MCM41 complexes, a stronger
bias (61%) toward the positive limit (P = 0.71) is observed
(Figure 47). This behavior is indicative of an increase in the
Figure 47. (A and B) Emission polarization (P) distribution
histograms for DY-630-MI interacting with MCM41 and with
AlMCM41 materials, respectively. Reprinted with permission from
ref 485. Copyright 2011 Royal Society of Chemistry.
number of more oriented single chromophores in the
nanochannel due to the modified electrostatic environment
around the encapsulated single molecule.485
In a study of the photoluminescence of defect centers in
single 11 nm SiO2 nanoparticles, it was suggested that a
strongly inhomogeneous local chemical environment around
the centers results in a broad and random variation of the single
nanoparticle emission and excitation spectra, fluorescence
Figure 48. Silver nanoclusters encapsulated in LTA and FAU sodalite cages, which are connected via the secondary building units (double 4-ring for
LTA and double 6-ring for FAU). Reprinted with permission from ref 486. Copyright 2016 Macmillan Publishers Limited, part of Springer Nature.
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lifetime, and quantum yield.478 Both the emission and
excitation spectra of different luminescent centers have shown
a shift within the range of 2.0−2.4 eV. Despite this broad
variation, the shape of the spectrum remains constant, which
suggests that the fluorescence comes from the same type of
defect and is a demonstration of the electronic nanoconfine-
ment effect on the properties of the luminescent defects in the
SiO2 nanoparticles.478
It has been shown that the rigid frameworks of zeolites can
act as a host in which silver clusters can be stabilized, enabling a
high degree of control over their optoelectronic properties
(Figure 48).486,487 The dependence of their electronic proper-
ties on spatial confinement was studied by characterizing the
ionization potential of the clusters embedded in four different
zeolite environments over a range of silver concentrations.487
The chosen faujasite frameworks (FAUX and FAUY) differ in
the Si/Al ratio of the framework, while the two LTA zeolites
(3A and 4A, Figure 49A) differ in the alkali metal charge-
balancing cation (Na+ and K+, respectively). The results reveal a
strong influence of silver loading and of the host environment
on the Ag cluster ionization potential (over a range of >0.5 eV),
which is also correlated with the cluster’s optical and structural
properties (Figure 49). Using zeolites as host, the photo-
luminescence quantum yields of the composites could be
optimized to reach nearly 100% by careful tuning of the
mobilities of nonframework metal cations.487
Single-molecule fluorescence and single particle tracking
methods reveal details of mass transport, catalytic reactions, and
molecular distribution in SBMs at the single-nanostructure and
single-molecule levels, while also providing information on their
physical morphology. Additional information on molecular
diffusion coefficients and degree of molecular confinement can
be obtained by using single molecule spectroscopy.
5. RECENT APPLICATIONS OF SILICA-BASED
MATERIALS
5.1. Photocatalysis
Micro- and mesoporous SBMs are widely used in the field of
catalysis.3,13,22,23,488 This is mainly due to the special and
interesting features of these materials such as their high surface
area, high thermal and hydrothermal stability, good adsorption
capacity, and the presence of actives sites, commonly Brønsted
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Figure 49. (A) Variation of the ionization potentials of the four calcined zeolites (FAUX[Ag11], FAUY [Ag6.5], 3A[Ag12], and 4A[Ag12]) loaded with
different contents of silver. (B) Peak emission energy change with the ionization potential for the studied zeolites. Reprinted with permission from
ref 487. Copyright 2016 Macmillan Publishers Limited, part of Springer Nature.
and Lewis acid ones.10,488 Furthermore, due to the dimensions
of their channels, these materials can also be selective toward
reactants, products, and/or transition states; as such, they can
be used for direct catalytic reactions while avoiding undesired
side processes (see Scheme 8 for molecules discussed in section
5). Acid and base catalytic reactions are used at a large scale in
the petrochemical industry for isomerization, hydrocarbon
cracking, and hydrocarbon synthesis.26,77,488−492 The catalytic
redox process generally occurs due to the presence of metal
atoms in the framework and results in the oxidation of the
reactant.22,26 Numerous reviews have reported on the use of
zeolites and mesoporous materials in catalytic reac-
tions.3,10,15,79,439−441 Therefore, in this review, we will highlight
only the most recent reports, predominantly those using light.
Photocatalytic reactions are initiated by light. In these
reactions, the encapsulated reactant is usually a photoactive
organic or inorganic molecule, although it can also be produced
by the presence of heteroatoms (Ti, V, and other transition
metals) in the micro- and mesoporous frameworks. Photo-
catalytic reactions are present in a wide variety of processes
such as the photoreduction of CO2 by H2O, the photocatalytic
oxidation of saturated hydrocarbons, the photosplitting of water
into hydrogen and oxygen molecules, and the photogeneration
of hydrogen peroxide, among others.18,493−498 All such
reactions are of great importance for the environment and
industrial chemical processes for the development of renewable
energy alternatives to fossil fuels.
In the presence of semiconductors and/or metallic atoms,
the SBMs can take part in photocatalytic degradation of the
encapsulated dye.499−505 For example, NaX zeolite impregnated
with Ag/AgCl−zerovalent iron particles (ZVIP) was prepared
for tetracycline (TC, Scheme 8) degradation.499 The reaction in
aqueous solutions under visible light is negligible due to the low
TC absorption in the visible range. However, the photocatalytic
efficiency of the composites is enhanced with the increase in
the ZVIP particles contents in the zeolite structure, displaying
maximum TC degradation when its weight ratio is 5%. Thus,
the TC and ZVIP interaction allows the formation of
composites with a strong absorption in the visible light region
and greater charge separation efficiency.499 Another report has
shown the degradation of norfloxacin in zeolite containing
silver oxide (Ag2O) and decorated with TiO2 (Ag2O/TiO2-
zeolite).500 Norfloxacin is an important antimicrobial drug but
with a potential risk to human beings and the environment. For
this reason, its photodecomposition has been evaluated in these
systems. In Ag2O/TiO2-zeolite composites, the photocatalytic
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process induces formation of •OH radicals, which leads to the
activation and acceleration of norfloxacin photodegradation.
The presence of Ag enhances the visible light absorbance and
provides better charge separation. Moreover, these composites
show high stability even after being used several times.500
Another photocatalyst formed by Ag was studied for the
photocatalytic degradation of MB (Scheme 4).501 In this
system, the MB interacts with thiol-functionalized MCM41
nanofibers (MCM41-SHNFs) in the presence of silver bromide
(AgBr).501 The photocatalytic reaction was observed at 664 nm
to follow the photodegradation and photodecolorization of
MB. In the absence of photocatalyst, the degradation of MB is
negligible. However, in the presence of AgBr/MCM41-SHNFs
composites and after 60 min under visible light irradiation, 87%
of MB is removed (Figure 50A).501 In the presence of AgBr
alone, the photodegradation process occurs with a lower
efficiency. Only 35% removal of MB after 60 min was observed.
This indicates that MCM41-SHNFs as a support plays an
important role in this photocatalytic reaction due to its ability
to adsorb more MB molecules on its surface, has more reactive
sites, generating larger amounts of free radicals during the
reaction, which contributes to the degradation of the MB
molecules. Furthermore, its presence prevents the photo-
corrosion of the AgBr semiconductor, granting an 87% removal
of MB even after five successive cycles (Figure 50B).501 AgBr/
MCM41-SHNFs composites showed higher stability with
respect to AgBr and other composites such as AgBr/SBA15,
AgBr/ZnO, and AgBr/TiO2.501,506,507
This reaction was also investigated using other mesoporous
materials, such as SBA15 containing TiO2 semiconductor
nanoparticles.502,503 The results showed an enhanced photo-
catalytic efficiency of MB decomposition, exhibiting rapid total
decolorization. Furthermore, doping SBA15 with Al atoms
(AlSBA15) creates a decolorization efficiency even higher than
those of TiO2/SBA15 and commercial TiO2. This was mainly
attributed to a more effective adsorption capability resulting
from the increased specific surface area after the substitution of
Si species with Al ones.503 Another recent report showed the
efficiency of a zeolite composite, graphene-Bi8La10O27-zeolite
(GBZ), for the degradation of MB and other dyes such as RhB
(Scheme 5) and Texbrite (TXB).504 For this composite, the
typical absorption peaks at 555, 665, and 360 nm for RhB, MB,
and TXB, respectively, decrease by 85, 87, and 83% after 5 min
of visible light irradiation. Their total degradation was observed
after 10 min. Upon visible light irradiation, high energy-
photoelectrons are detected in the zeolite composites, whose
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Scheme 8. Molecular Structures of the Compounds Interacting with SBMs and Discussed in the Applications Section 5

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Scheme 8. continued

Figure 50. (A) Changes in the UV−visible absorption spectra of MB showing the photodegradation under visible light irradiation in the presence of
AgBr/MCM41 SHNFs nanocomposites. (B) Cycling degradation efficiency of MB solution in the presence of AgBr nanoparticles and AgBr/
MCM41 SHNFs nanocomposites. Reprinted with permission from ref 501. Copyright 2016 Elsevier B.V.

Figure 51. Schematic representation of graphene-Bi8La10O27-zeolite nanocomposite, showing a high photocatalytic efficiency activity toward organic
dyes degradation. Reprinted with permission from ref 504. Copyright 2017 Elsevier B.V.

formation leads to the generation of •OH radicals that are
responsible for the photodegradation of the free dyes (Figure
51).504 The photodegradation of rhodamine molecules in
aqueous solutions with TiO2-chabazite materials was also
investigated.505 For these composites, 90 min of light
AW
irradiation were necessary to cause the almost total degradation
(∼98%) of rhodamine. The photocatalytic process is initiated
when TiO2 absorbs the UV radiation, generating electron−hole
pairs on the zeolite composites. The high oxidation potential of
the hole in the catalytic surface and the presence of •OH
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radicals cause the dye photodegradation but with an efficiency
lower than in the case of GBZ.505 This is explained in terms of
higher molecular adsorption capacity of GBZ, as this system
contains two different surfaces (graphene-Bi8La10O27 and
zeolite) for the adsorption of the molecule, which can absorb
more light and generate more electron−hole pairs to remove
the dye pollutant molecules.
The use of micro- and mesoporous composites containing
TiO 2 presents remarkable advantages due to its easy
preparation, low cost, and chemical stability.508−511 A recent
study reported on the adsorption capacity of TiO2 immobilized
in a zeolite framework for humic acid detection and extraction
from water.512 In the absence of TiO2, the natural zeolite
showed a low affinity for humic acid, while in its presence, the
formed composite was an effective adsorbent that removed the
humic acid fraction with high aromaticity and molecular weight.
Furthermore, the TiO2/zeolite composites are readily regen-
erated by UV light irradiation, so that the adsorption capacity is
maintained even after five successive adsorption−regeneration
cycles.512 Another report presented the photodegradation
reaction of acetaldehyde gas in the presence of TiO2/zeolite
type X (Figure 52).513 The results demonstrated that the
photocatalytic decomposition activity in TiO2/zeolite X was
higher than in TiO2 nanoparticles.513
Figure 52. Schematic representation of the photodegradation reaction
of acetaldehyde gas in the presence of TiO2/zeolite X. Reprinted with
permission from ref 513. Copyright 2013 Springer.
A similar result was observed for the photodegradation of
methanol gas using TiO2/β-zeolite and TiO2/SBA15 materials,
where the reaction efficiency was higher than in conventional
P25-TiO2 commercial nanoparticles.514,515 The result was
explained in terms of a higher photocatalytic activity of TiO2
when it is supported, as the micro- and mesoporous structures
improve the separation of the electron−hole charges formed in
the semiconductor under irradiation. Furthermore, the acidity
and the presence of active sites on the surface of these materials
lead to a high adsorption of organic compounds and an increase
in their photoreactivity. Another report showed the photo-
catalytic activity of zeolite Y impregnated with different
amounts of TiO2 in the degradation of p-nitrotoluene (PNT,
Scheme 8) in aqueous media.516 The degradation of PNT
adsorbed in these composites gives rise to a mineralization
resulting in simple final products: CO2, H2O, NO3−, and NH4+.
The activity of this photocatalytic process depends on the
amount of TiO2 in the zeolite structure. A low loading of TiO2
leads to a lower generation of charge-separated states and
therefore less photodegradation, while a high loading can block
the zeolite pores, resulting in a decrease in the adsorption
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capacity of the catalyst for PNT. Thus, an optimal loading of 2
w/w % is necessary for these composites to reach their
maximum efficiency.516 This efficiency was improved with the
copresence of Ag ions in the zeolite framework, as Ag particles
help to generate a higher charge separation and thus improve
the photocatalytic activity of the catalysts. This was also
observed in other systems used for the photoreduction of water
to hydrogen and oxygen molecules.517 The coupling of the
TiO2 semiconductor nanoparticles present in zeolite Y with a
metal (Pt) and another semiconductor (CdS) has a stronger
influence on the photocatalytic activity of the formed
composites. The hydrogen evolution rate improves by a factor
of 100 and 18 when Pt and CdS were incorporated to the TiO2-
zeolite Y system, respectively.517 It is worth noting that to
obtain these results, the titanium, which is part of the zeolite
framework, has to be in intimate contact with Pt or CdS. For
this reason, in the Pt/CdS/TiO2-zeolite Y ternary system,
where the localization of nanoparticles is mediated by the
zeolite via a self-assembly process, the improvements in the H2
evolution rate were not as marked because Pt was not in direct
contact with TiO2.517 Another system composed of titania and
iron-exchanged zeolite was used for the photodegradation of
diclofenac (DCF, Scheme 8).518 This anti-inflammatory drug is
a pollutant that, when present in water, adversely affects human
health and the environment. DCF adsorption onto TiO2−FeZ
surfaces and the subsequent irradiation leads to its photo-
degradation.518 However, the generated photoproduct tends to
accumulate on the TiO2−FeZ surface, thus negatively affecting
the subsequent photocatalytic cycles. Therefore, thermal and
chemical reactivation strategies were necessary to improve the
photocatalyst stability in reuse cycles of these systems. Thermal
treatment at 553 K produces an increase in the activity of
consecutive cycles due to a high DCF and total organic carbon
(TOC) removal rate and an increase in TiO2 crystallinity. A
chemical treatment using ozone flow also increased the reuse of
this material, although with an activity lower than in the
previous treatment.518
The combination of SBMs and some organic or inorganic
compounds also gives rise to formation of active photocatalytic
systems.519−521 For example, tungstosilicic acid (TSA, Scheme
8) immobilized on NH4Y and NH4ZSM5 zeolites was used for
the photodecomposition of methyl orange (MeO, Scheme
8).519 Heteropolyacids (like TSA) were used as photocatalysts
in the degradation of organic pollutants present in water due to
their nontoxicity and high photostability. These compounds
showed photocatalytic properties comparable to semiconduc-
tors such as TiO2, ZnO, and CdS. However, these systems
cannot be used directly in catalytic reactions because they have
low surface area and high solubility in polar solvents, which
makes them impossible to reuse. When supported in zeolite
materials, the photocatalytic system increases its specific surface
area and allows their easy recovery and reuse.519 The amount of
TSA (% w/w) on the zeolite surface also affects the efficiency
of the photocatalytic reaction. After 240 min with 5% w/w
TSA, the photocatalytic system removes 28% of MeO, while
with 30% w/w and in the same time range, the photo-
degradation process was improved, reaching 75% removal.519
However, despite being supported, this system showed a low
reuse capacity, with the catalytic efficiency decreasing from 75%
to 36% in the second cycle. This is due to the adsorption of the
reaction products on the catalyst surface, decreasing the
number of actives sites available for the absorption of the
initial reactant.519 Another composite formed by cobalt
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Figure 53. (A) Fluorescence spectra of RhB in tetraphenylethene-bridged periodic mesoporous organosilica particles at different dye contents. (B)
CIE chromaticity coordinates showing the emission colors of the films (dots). Reprinted with permission from ref 525. Copyright 2015 Royal
Society of Chemistry.
phthalocyanine (CoPc, Scheme 8) immobilized onto MCM41
was used for the degradation of MeO.520 After 2 h of visible
light irradiation, the photodegradation process was completed,
with a removal rate of 99%. This photocatalytic efficiency is
much better than that observed in the previous study and in
another system formed by a semiconductor, CuO, incorporated
in zeolite X, where only 60% of the dye was removed under the
same experimental conditions.522 Furthermore, CoPc/MCM41
systems exhibited high photostability, being useable for four
consecutive cycles, with the MeO degradation process only
decreasing from 99 to 90%.520 These results revealed that the
use of SBMs as support and reaction hosts provides high
stabilization for the organic and inorganic guests in addition to
preventing their molecular aggregation, so improving their
catalytic activity.
5.2. Photonics
One of the most important issues in photonics field is the study
and development of light sources. The application of silica-
based hosts in designing efficient, broadband, and stable light
sources has great potential. First, as we already commented and
highlighted, encapsulation of organic and inorganic fluoro-
phores can enhance their emission as a result of suppression of
the nonradiative deactivation processes (see sections 2 and 3).
Furthermore, as commented on in this review silica hosts
enable the coloading of chromophores emitting in different
spectral regions, facilitating broadband lighting sources. Finally,
encapsulation usually provides protection against the outside
environment, which is important for improving the stability of
the light source. A few recent examples of the above strategies
will be outlined below. The examples are grouped into four
categories, depending on the nature of the guest species:
molecules, rare earth elements, silver clusters, and perovskites.
The studies of dye-doped silica nanoparticles before 2010
were reviewed in another report.373 A system with ruthenium
tris-bipyridyl encapsulated inside zeolite Y supercages was
tested for use in electrochemiluminescent cells.523 The
synthesis of the ruthenium tris-bipyridyl complex was achieved
by a ship-in-a-bottle method. The cell operated at an optimum
voltage of 3 V. The electrochemiluminescent efficiency of the
cell was significantly increased upon the ion exchange of
sodium with cesium and the vapor deposition of calcium metal
inside the zeolite pores. Generally, in such configurations, each
nanoparticle can contain several active molecules, allowing very
high absorption coefficients (>106 L mol−1 cm−1) and
luminescence quantum yields. Moreover, multichromophoric
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systems can show collective EnT and ET with possible
functions such as signal amplification and light harvesting.
More recently, mesoporous silica nanoparticles of 50 nm in
diameter were prepared containing two chromophores that
emit in different spectral ranges.524 One of them was the Zn
complex of HBT (Scheme 3), emitting blue light, while another
was the orange-red dye RhB (Scheme 5). By choosing the
concentrations and ratio of these two fluorescent centers, a
nearly white light-emitting system was produced.
The coupling of two chromophores of opposite fluorescence
behaviors was also realized in periodic mesoporous organo-
silicas.525 Blue-emitting tetraphenylethene-bridged organosilane
was used as a precursor for preparing high-performance
luminescent nanoparticles. These NPs avoid the typical
fluorescence quenching and thus are aggregation-induced
emission materials. RhB (which exhibits aggregation-induced
quenching) was then encapsulated in the nanoparticle as an
energy acceptor partner. The emission of the resulting
composites could be fine-tuned over the entire visible spectrum
by adjusting the content of the encapsulated RhB dye, as
illustrated in Figure 53. Highly pure solid-state white light was
achieved with a quantum yield of nearly 50%.
In another contribution, the aggregation-induced emission
molecule coded CWQ-11 (Scheme 8), a carbazole-based
cyanine molecule, has been doped in situ into SiO2 NPs.526
The fluorescence of such molecules is closely related to their
restricted structure. Inorganic silica NPs provided a rigid
microenvironment that stabilized CWQ-11 molecules to obtain
fluorescent materials exhibiting almost 50 times higher
quantum yield than that for the same molecule in solution.
Both one- and two-photon fluorescence was studied for
hemicyanine molecules encapsulated in nanosized silicalite-1
zeolite.527 It was found that one- and two-photon absorption
coefficients were the same for the dye in solution and inside the
zeolite. However, significant differences were found in the
fluorescence quantum yields where the one-photon fluores-
cence was enhanced 5 times, while the two-photon signal was
enhanced 3.3 times upon encapsulation.
Lanthanide ions possess unique and attractive optical
properties such as sharp and long-lived emission in the visible
to near-infrared (NIR) region with high color purity. However,
their practical application is hindered by their poor physical
stability, which can be overcome by immobilization in SBMs.
The luminescence properties of zeolite functionalized with
lanthanides were recently reviewed.528 In addition to improved
thermal stability and photostability upon encapsulation, other
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Figure 54. (A) Emission of Eu3+ in zeolite supercages induced by UV irradiation upon washing with the indicated solvents and calcined. Reprinted
with permission from ref 528. Copyright 2014 Royal Society of Chemistry. (B) Electroluminescence spectra of ZEOLED (silver-exchanged zeolites)
at different applied voltages. Reprinted with permission from ref 530. Copyright 2017 Wiley-VCH.

Figure 55. (A) Emission decays of CsPbBr3 nanocrystals synthesized within meso-SiO2 of different characteristic size. The inset shows the sizes of
the crystals. Reprinted from ref 533. Copyright 2016 American Chemical Society. (B) Normalized emission spectra of MAPbI3 nanocrystals grown
using templated TiO2 (orange) and SiO2 (purple) porous films as scaffolds. Gray dashed spectrum corresponds to the photoemission of a flat
perovskite film. Reprinted with permission from ref 537. Copyright 2017 Wiley-VCH.

new properties of lanthanides were also reported, including
spectrally tunable luminescence and emission enhancement
upon annealing (Figure 54A). Moreover, multicolor-emitting
lanthanide complex-loaded zeolite materials could be fabricated,
and transparent luminescent composites could be created by
embedding nanosized Ln3+‑functionalized zeolites into poly-
(methyl methacrylate) (PMMA) matrices. Even more complex
hybrids were proposed based on incorporating a rare earth
ternary complex into CdS QDs-loaded zeolite Y through a
coordination reaction.529 The highest luminescence quantum
yield was obtained for the system consisting of CdS−zeolite
functionalized with europium, mercaptoacetic acid, and 1,10-
phenanthroline ternary complex, with a lifetime of almost 1 ms.
An interesting alternative to the above luminescence
materials was recently proposed based on silver clusters
incorporated in a zeolite matrix.531 Direct evidence at an
atomic level of luminescent silver species stabilized in faujasite
zeolites was presented using scanning transmission electron
microscopy (STEM). Two different silver clusters were
identified: a trinuclear silver species associated with the green
emission, and a tetranuclear silver species associated with the
yellow one. A nonluminescent state associated with Ag3 species
was found to be a precursor for the subsequent formation of
luminescent Ag clusters upon heat treatment. Stable
luminescent silver clusters were also observed in sodalite
cages of hexagonal analog faujasite type zeolite (EMT).532 The
octamer (Ag8) was proposed as one of the most stable clusters
and exhibited molecular-like emission properties with an
emission band at 395 nm and a nanosecond decay time. A
AZ
second emission band at 545 nm with a much longer lifetime
(microsecond time scale) was attributed to charged silver
species. Introducing luminescent silver-exchanged zeolites into
a conductive polymer matrix as emitters resulted in new
electroluminescence bands.530 The successfully constructed
devices were called ZEOLEDs. Their electroluminescent
spectra showed additional emission bands besides those present
in photoluminescence (Figure 54B). The emission color of this
system [Commission Internationale de l’Éclairage (CIE)
coordinates] could be tuned from blue to red color by
changing the silver concentration in the zeolite framework.
Perovskites emerged as new and very promising materials for
photovoltaics. A few examples of combining SBMs with
perovskites for solar cells application will be presented in the
next section 5.3. Simultaneously, the slow charge recombina-
tion and excellent charge transport properties of perovskites are
also very promising in luminescence applications. A few
strategies to employ silica templates to improve such
luminescence properties will be outlined below.
In one of the first such reports, a large variety of perovskite
compounds, hybrid and fully inorganic, were studied.533 With
the general perovskite formula APbX3, the materials were tested
in which A was cesium (Cs), methylammonium (MA), or
formamidinium (FA), and X was Cl, Br, I, or a combination
between two of them. Various commercially available
mesoporous silica templates of pore sizes ranging from 2.5 to
50 nm were used to encapsulate the zeolite QDs. These were
synthesized inside the pores by infiltration of the precursor
solutions, and then after drying, template-assisted perovskite
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Figure 56. (A) SEM images of zeolite L monolayers, and zoomed region of the composite containing two dyes and modified with a stopcock.
Reprinted with permission from ref 388. Copyright 2008 Royal Society of Chemistry. (B) Schematic representation of energy transfer (EnT) process
in a chromophore embedded in periodic mesoporous organosilica. Reprinted with permission from ref 542. Copyright 2014 Royal Society of
Chemistry.
nanocrystals were formed. This simple method led to a high
emission quantum efficiency exceeding 50%. In Figure 55A, an
example of testing trapped CsPbBr3 crystal in SBMs is shown,
for which the longest perovskite lifetime (the most luminescent
composite) was observed in the silica material of 7 nm pores
(hexagonally ordered 1D-channels known as MSUH meso-
phase).
Green-emitting CsPbBr3 crystals were also mixed with
mesoporous silica of pore sizes 12−15 nm to prevent the
anion-exchange effect.534 The composite was then mixed with
red CsPb(Br0.4I0.6)3 nanocrystals in silicone resin and then
dropped in the blue InGaN chip to yield a LED device for
backlight display with high stability and wide color range.
Furthermore, green CsPbBr3 and red CsPb(Br/I)3 crystals were
used to prepare the composites that gave efficient and stable
white LEDs.535 The polyhedral oligomeric silsesquioxane
enhances the performance of a LED device based on
CsPbBr3.536 The result was explained in terms of hole-blocking
properties of the silica-based layer, which keeps both electrons
and holes located within the active perovskite layer for more
efficient recombination.
A well-known problem of hybrid perovskites is their
instability when interating with water molecules (humidity in
air). The protection of MAPbBr3 nanocrystals from moisture
was studied using silica coating.538 A novel method of
preparation of the SiO2 layer was proposed, since the
conventional silica formation method required water.539 On
the contrary, the new preparation method using toluene
without ligand exchange yields remarkable photostable silica-
encapsulated perovskite (94% photoluminescence quantum
yield after 7 h of irradiation). MAPbBr 3 and MAPbI 3
perovskites were confined in a gyroidal mesoporous silica
template of various sizes from 5 to 12 nm.539 The crystal
structure and optical properties (absorption edge and emission
maximum) show a consistent change as the particle size is
reduced. Quasi-2D, 2D, and 3D perovskites (MAPbBr3) were
stabilized in MCM41 matrix.540 All the formed composites
exhibit strong photoluminescence. The electroluminescence
signal was also observed and attributed to EnT from higher
bandgap perovskites (quasi-2D, 2D) toward lower band gap
perovskites (3D). MAPbI3 perovskite nanocrystals (1−4 nm
diameter) were grown within periodically mesostructured films
of TiO2 and SiO2.537 Tunable quantum confinement effects
were observed due to the dimensions of nanocrystals
comparable to the exciton Bohr radius. For example, a large
blueshift of the emission intensity maximum was observed over
a wide range of 0.34 eV (Figure 55B). This result demonstrates
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that perovskite nanocrystals can become stable visible light
emitting materials at a desired spectral region.
Another branch of photonics with interesting applications of
SBMs is in light transmission media. The most explored silica-
based material in this context is probably zeolite L. Its crystals
can contain oriented fluorophores in their parallel nano-
channels. They then possess remarkable fluorescent properties
and can be arranged in nearly any desired manner via self-
organization methods.388 FRET between encapsulated dyes is
the mechanism responsible for energy transport along the
channels. Communication between the chromophores located
inside the host and the outside world is realized via stopcock
molecules of different shape, size, and nature (Figure 56A). The
dynamics of the EnT processes in SBMs were presented in
section 3.3, and some of the theoretical results were described
in section 2.2. It was demonstrated that it is possible to obtain
well-organized dyes in zeolite L material in which FRET
efficiency can be modulated by selecting suitable dye
combinations (with a special attention to the spectral overlap
of donor emission and acceptor absorption).16 Several levels of
organization have been realized for zeolite L, extending from
the interior of a given crystal to the channel entrances and the
external surface, as well as from the microscopic to the
macroscopic space domain.541 Recently, a variety of new dyes
from the perylene diimide, terrylene, and quaterrylene family
were tested for supramolecular organization in zeolite L
channels.385 Plugging the channel prevents the guests from
escaping to the outside environment, which is essential for
achieving long-term stability of such composites. The dye-
zeolite L composites were also inserted into polymer matrices
and maintained their optical transparency.
In addition to zeolite L, another SBM for light harvesting and
transport is the PMO, which is formed via polycondensation
between organosilane precursors.542 The organization of the
chromophores in the PMO wall, along with appropriate guest
molecules in their meso-channels, make a versatile donor
scaffold for the EnT process (Figure 56B). It should be noted
that artificial antenna systems based on zeolites have also been
proposed for application in photovoltaics and other solar
energy conversion devices. Other aspects of the potential use of
SBMs in solar cells will be briefly presented in the section 5.3.
5.2.1. Sensors. Host−guest systems based on SBMs can
also be used as sensors. A sensor is defined as an entity
(molecule or material) that can detect changes in its
environment, altering its properties as a result. Changes in
fluorescence intensity, in particular, are considered the most
effective tool for sensing applications due to their high
sensitivity, easy visualization, and short detection response
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time. Sensors fabricated by encapsulating a fluorescent probe in
SBMs have demonstrated interesting properties such as high
thermal and mechanical stability, high brightness, photo-
stability, and relatively low cytotoxicity.8,543
With dependence on the analyte of interest, many types of
sensors can be found. pH Sensors are some of the most in
demand mainly due to their applications in biomedical
diagnosis.14,19,544−546 These sensors are fabricated with pH-
sensitive fluorophores encapsulated in or interacting with micro
or mesoporous materials. For example, spectroscopy techniques
have demonstrated the good pH sensitivity of a sensor based on
zeolite-β encapsulating 3-HF with a shell of amorphous silica
with fluorescein isothiocyanate (FITC, Scheme 8) mole-
cules.545 The experimental results demonstrated that this
sensor has high sensitivity, stability, and real-time response
for pH changes. While the caged 3HF did not show significant
changes in the pH range of 5−8, the fluorescence signal of the
fluorescein embedded in the amorphous silica shell was
strongly affected, reaching its maximum value at pH = 8.545
Another study reported a sensor formed by mesoporous silica
nanoparticles (MSNs) doped with R6G-lactam (Scheme 8) and
FITC.546 The R6G-lactam shows strong fluorescence in acidic
media, while FITC exhibits the opposite behavior, exhibiting its
maximum fluorescence intensity in basic media. This dual
colored sensor was characterized in the presence of sodium
phosphate buffers of various pH (3.5−7.5). At acidic pH (3.5),
the emission spectrum has an intensity maximum at 552 nm
(rhodamine-lactam intensity maximum), which decreases at
higher pH values with a simultaneous increase in the
fluorescence signal at 515 nm (FITC intensity maximum).546
This favorable inverse pH response improves the sensitivity of
this sensor. The lysosome acidity range (3.5−5.5) overlaps with
the optimal sensing range of this nanosensor (3.5−6.0),
suggesting that it could be used to monitor cell acidity and in
lysosome-targeted cancer therapy.546 A similar system, formed
by hollow mesoporous silica nanoparticles (HMSNs) doped
with rhodamine B isothiocyanate (RITC, Scheme 8) (pH
insensitive) and FITC (pH sensitive), has been investigated to
monitor intracellular pH.547,548 Its fluorescence spectrum shows
an increase in the intensity maximum of FITC (at 514 nm) at
high pH values, while the intensity maximum of RITC (at 576
nm) remains nearly constant.547,548 With the use of the change
of the ratio of the emission intensity of both dyes with the
variation of pH values, a pH calibration curve was obtained
whose pH response ranges are 4.5−8.5. This pH sensitivity
range is broader than those of systems based on MSNs (3.5−
5.5) due to the larger pore size of HMSNs (2.9 nm vs 2.1 nm
for MSNs) and the broader surface curvature distribution.547,548
An extension of the pH response between 3.2−9.0 was possible
by tuning the thickness and pore size distribution of these
systems, making them one of the best candidates for pH
sensors.548 Another report has shown a new pH sensing device
formed by mesoporous MCM41 materials functionalized with a
novel Ru(II) complex of Ru(Bphen)2PIP (Bphen = 4,7-
diphenyl-1,10-phenanthroline and PIP = 2-phenyl-1H-imidazo-
[4,5-f ] [1,10]phenanthroline).549 When excited at 460 nm,
these composites display an emission signal with an intensity
maximum at 602 nm, which decreases with increasing pH
values (1.07−12.92) (Figure 57).
At low pH values (1.07−4.22), the PIP ligands of the Ru(II)
complex are protonated, inducing emission from the Ru(II)
center. At even higher pH values (4.22−6.64), the PIP ligands
undergo deprotonation, leading to an increase in the non-
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Figure 57. Emission spectra of Ru-MCM41 in water solutions at pHs
from 1.07 to 12.92. Inset (up): emission intensity change with the pH
value. Inset (down): fitted working plot (red line) in a pH range of
4.22−6.64. Reprinted with permission from ref 549. Copyright 2014
Elsevier B.V.
radiative decay of Ru(II) and the quenching of its emission
signal. From pH 7.16 to 11.07, the emission signal is stable
because the PIP ligands are present in their neutral forms and
no effect on the fluorescence of the Ru(II) center was observed.
However, when the pH is higher than 12, the deprotonation of
the PIP ligands leads to an increase in their electron density,
further favoring the nonradiative decay pathways and thus
quenching the fluorescence of Ru(II).549 These results have
demonstrated that the most sensitive pH region for this sensor
was 4.22−6.64, which could be related to the mesoporosity of
the MCM41 materials, as it favors the OH-diffusion to the
complex, resulting in quick quenching of its emission.549
Optical sensors for the detection of organic molecules and
metal cations have been recently investigated. For example, an
experimental study demonstrated the sensitivity of mesoporous
organosilica films with 2D-hexagonal symmetry (p6mm)
structure to the presence of the explosive TNT (Scheme
2).50 The system is formed by naphthalene-bridged silane
(BTPN, electron D, Scheme 8), which exhibits an ET process
with TNT (electron-A). The sensing rate was characterized by
fluorescence experiments, as the adsorption of TNT molecules
on these composites quenched the emission signal.50 The study
showed that the sensitivity and selectivity of this sensor could
be improved by modifying the pore length and adjusting the
rate of TNT adsorption, respectively. Thus, the mesoporous
material directly affects the properties of the sensor. Similar
behavior was observed for a system formed by mesoporous
silica thin films containing a phenyl-substituted pyrene
fluorophore (TKMPP, TKHPP, and TKSPP, Scheme 8) as a
sensor of another nitroaromatic compound, 2,4-dinitrotoluene
(DNT, Scheme 8).550 The mesoporous architecture (wormlike,
2D- and 3D-hexagonal mesopores) in the presence or absence
of the amphiphilic surfactant P123, and the mode of
introduction of the fluorophore (bonded or impregnated on
the framework) influenced the detection range of the fabricated
sensor. In mesoporous films doped with pyrene dye and in the
presence of the surfactant P123, different efficiencies were
observed according to the structure of the mesoporous films.
Quenching levels of 45% and 9% were reported at 45 s for the
wormlike and 2D-hexagonal structures, respectively; while a
lower quenching of 28% for the 3D-structures at 90 s was
recorded.550 In fluorophore-bridged films and in the presence
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of surfactant, the reported quenching was lower for all
structures, reaching emission quenching efficiencies of 8.5%
and 3% after 30 s for the wormlike and 2D-hexagonal
structures, with no detected changes for the 3D-hexagonal
structure. However, in the absence of P123, these composites
show the best quenching performance, with 72% and 14%
quenching after 30 s for the wormlike and 2D-hexagonal
structures, respectively.550 The detection of other pollutants
such as ethylenediamine (En) is of great importance for
chemical industries due to its potential threat to human health.
Another report studied a selective sensor for En formed by
zeolite Y (ZY with terbium-acetylacetone (Tb(acacn))
complexes in their cavities.551 The Tb(acacn)/ZY composites
showed considerable changes in luminescence color in the
presence of En vapor. Figure 58 shows the CIE chromaticity
Figure 58. CIE chromaticity coordinates of Tb(acacn)@ZY upon
exposure to various solvent vapors for 10 min. Reprinted with
permission from ref 551. Copyright 2016 Elsevier B.V.
coordinates in the presence of En (0.21, 0.22) and other
solvent vapors (in the range from 0.26, 0.33 to 0.31, 0.49),
demonstrating the excellent selectivity of these composites for
the detection of En.551
In addition to good selectivity, this sensor also shows high
sensitivity. To demonstrate it, experiments with different
concentrations of En in the presence of other solvents such
as Et3N, n- and t-BuNH2, benzylamine, and methyaniline were
performed, revealing a detection limit of 2% (volume ratio)
Tb(acacn)ZY.551 A similar system formed by zeolite L
functionalized with Tb-2-thenoyltrifluoroacetone (Tb-TTA)
complexes was used for luminescent sensing of dipicolinic acid
(DPA, Scheme 8), which is the main constituent of many
pathogenic bacteria.552 The intensity of the Tb(III) lumines-
cence increased upon increasing the concentration of DPA due
to the formation of a Tb-TTA-DPA complex. This sensor
showed good selectivity and sensitivity, detecting DPA even at
relatively low concentrations (0.05 μM).552 Another system
based on zeolite A with a lanthanide complex was used for the
selective detection of metal ions.553 This composite was formed
by ytterbium-1,3-diphenylpropane-1,3-dione (Yb-DBM) com-
plexes within the zeolite cavity and europium-1-(2-naphthoyl)-
3,3,3-trifluoroacetonate (Eu-NTA) ones bonded on the zeolite
surface. The behavior of the [DBM-Yb-ZA]-NTA-Eu compo-
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sites was examined in the presence of different metal ions such
as Ag+, Na+, K+, Pb2+, Al3+, Mg2+, Zn2+, Cd2+, Hg2+, Co2+, Fe3+,
Ni2+, and Cu2+, strongly detecting the last four cations, most
notably Fe3+, in the presence of which the emission signal was
strongly quenched.553 The selectivity of this system toward
metal ions arises mainly from the exchange interaction between
these and zeolite A hosts. The fluorescence response range was
determined with different concentrations of Fe3+ (up to 1
mmol L−1), observing that the luminescence intensity of Eu3+
decreased with the increase in [Fe3+], reaching a total
quenching at 1 mmol L−1. The detection limit was 0.224
mmol L−1.553 This value is higher than that reported for
another sensor composed of a hybrid mesoporous silica
functionalized with a silane derivative porphyrin (TPP) and
quinolone.554 In addition to detecting Fe3+, this hybrid material
is also sensitive to other trivalent metal ions such as Cr3+ and
Al3+. The presence of these ions simultaneously quenched the
TPP emission (650 nm) and enhanced the fluorescence of
quinolone (∼500 nm), causing a change of emission color from
red to green (Figure 59).554 The hybrid composites showed
Figure 59. Variation in the fluorescence intensity ratios (I650 nm/
I500 nm) of mesoporous silica (20 mg mL−1) with the concentrations
of Fe3+, Cr3+, and Al3+ ions in ethanol solutions. The inset shows the
fluorescence color changes. Reprinted with permission from ref 554.
Copyright 2016 Wiley-VCH.
low detection limits of 0.08, 0.1, and 0.2 mmol L−1 for Fe3+,
Cr3+, and Al3+, respectively (Figure 59). The different response
degrees to Fe3+, Cr3+, and Al3+ allow the use of this material for
the simultaneous detection of these three ions.554
SBMs have also been used as humidity sensors. A recent
report demonstrated a remarkable dynamic change in the
emission color of Ag-LTA zeolite in the presence of water.555
These composites were investigated following thermal treat-
ment (Figure 60). At room temperature, a broad band centered
at 600 nm was observed. However, after heating, the
fluorescence of the zeolite composites was different. At 473 K
(approximately 20 water molecules per normalized unit cell),
the zeolite composites show the most remarkable changes with
the presence of three well-defined emission bands at 560, 470,
and 390 nm. At 573 K (approximately 10 water molecules per
normalized unit cell), the emission band at 560 nm disappears
and the 470 and 390 nm bands blue-shifted. At 723 K
(approximately 1 water molecule per normalized unit cell), only
an intense blue emission band is detected. Therefore, the fully
hydrated composites (20% water content) show a yellow
emission, whereas partially hydrated samples (17−3% water
content) present green and blue emission, and finally, the
samples with less than 1% water content display only blue
emission, thus demonstrating high sensitivity toward the
presence of water molecules in the Ag-treated zeolite cages.555
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Figure 60. (A) Emission spectra of LTA(Li)−Ag1 after heat-treatment at different temperatures. (B) Color change of real samples with respect to
water content illustrated by the blue arrow. Reprinted with permission from ref 555. Copyright 2015 Royal Society of Chemistry.

Figure 61. (A) Schematic representation of the titanium clusters in the zeolite supercages. Reprinted with permission from ref 561. Copyright 2006
Wiley-VCH. (B) Illustration of the operation principles of DSSCs based on titanium-containing zeolites. Reprinted with permission from ref 562.
Copyright 2007 Wiley-VCH.

The systems with silica-coated chromophores were also
proposed in sensor applications, with the operation based on
EnT mechanism. Rhodamine-doped silica nanoparticles were
linked to amphiphilic black hole quenchers to form a probe of
reductive environments in living cells.556 Depending on the
number of quenchers adsorbed on each particle, the
fluorescence lifetime decreased from 3.7 ns (no quenchers)
to 1.9 ns (16 quenchers per particle). The fluorescence
quenching, due to FRET, did not occur in the presence of
reductive agents. As a result, these silica-based NP probes
showed more than a 10-fold increase in their fluorescence
intensity in a reductive environment. Rhodamine dye was also
doped within relatively large silica NPs (160 nm diameter).448
A very high fluorescence quantum yield and single lifetimes of
nanoseconds were reported despite the dye concentration
within each nanoparticle exceeding the typical value of
dimerization in water. The absence of concentration quenching
effect was explained by the lack of water leakage through silica
walls and the presence of CTAB surfactant inside the particles
as a splitting element among the dye molecules. This system,
which exhibits a super fluorescence, was suggested as a
promising candidate for imaging and labeling applications.
Core−shell nanoarchitectures were used to study FRET
between a luminescent Tb3+ chelate, N,N,N1,N1-[4′-phenyl-
2′2′:6,′2′-terpyridine-6,6′-diyl]bis(methylenenitrilo)tetrakis-
(acetate)-Tb3+ (PTTA-Tb3+), and an organic dye, 5-carboxyte-
BD
tramethylrhodamine (CTMR, Scheme 8).557 A CTMR-SiO2
core was surrounded by concentric PTTA-Tb3+-SiO2. The long
emission lifetime of the donor (PTTA-Tb3+), 1.21 ms, was
reduced to 246 μs in the core−shell structure, which resulted in
a very efficient EnT to CTMR with a quantum yield of 80%, in
agreement with the results calculated from the areas of the
corrected sensitized emission curves.557 DY-630-MI (Scheme
7) was covalently encapsulated in the core of ∼20 and ∼30 nm
core−shell silica nanoparticles.558 An approximately 15-fold
increase in the fluorescence intensity was reached, which is
ascribed to restriction of the isomerization process in the dye’s
excited state and the protection from solvent interactions. FCS
revealed that energy hopping between the dye molecules within
the single nanoparticles can occur. This process was found to
be more efficient in smaller (∼11%) than in bigger (∼5%)
nanoparticles.558 In another study, a sensitizer (octaethylpor-
phyrin Pd complex) and an annihilator (9,10-diphenylanthra-
cene, Scheme 8) were coloaded into silica nanoparticles to give
blue-emissive up-conversion nanoparticles.559 The sensitizer
absorbs green light and transfers the energy to the triplet states
of the annihilators. When the triplet−triplet annihilation
process occurrs, it results in the final excitation of the blue-
emitting singlet state. This silica-coated system showed low
cytotoxicity and was successfully used to label living cells with a
very high signal-to-noise ratio.
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Figure 62. (A) Schematic representation of ET from excited TPC1 to titania-containing mesoporous structures (not to scale). Reprinted from ref
564. Copyright 2011 American Chemical Society. (B) Current−voltage curves of DSSC with TPC1 dyes attached to titania nanoparticles and
TiMCM41 material (with 6.3% Ti doping) under 50 mW/cm2 illumination. Reprinted from ref 326. Copyright 2011 American Chemical Society.
5.3. Photovoltaics
Silica is an excellent insulator with a high dielectric strength
(107 V/cm) and large band gap (8.9 eV). Therefore, its direct
use in photovoltaics as a photoactive material or charge
transporter is rather limited. However, the very high specific
surface area of micro- and mesoporous SBMs, the doping
ability that can drastically modify their material properties, and
the possibility of using SBMs as various templates do provide
routes for the potential application of SBMs in photovoltaics.
Below, few examples of attempts to use silica materials in dye-
sensitized solar cells (DSSCs), QDs and perovskite solar cells
are presented.
A key element in DSSCs is the interaction of dyes with a
network of semiconducting metal-oxide nanoparticles (usually
TiO2).27,560 Such materials constitute a layer with a high
specific surface area, allowing sunlight to be efficiently
harvested by the attached dyes over distances of few microns.
Moreover, TiO2 is also a medium that can transport electrons
injected from the excited dye into its conduction band.
Therefore, interest in using SBMs in DSSCs has been
correlated with the successful doping of SiO2 frameworks
with TiO2. One of the first attempts was the incorporation of
discrete clusters of TiO2 within the internal micropore space of
zeolite Y.561 The clusters contained only a few titanium atoms
(Figure 61A), with Ti loading of 4.8 wt %. In contrast to the
inactive zeolite Y matrix, all the zeolite encapsulated TiO2
species showed a photovoltaic response when irradiated with 1
sun illumination (100 mW/cm2, spectrum of AM1.5 standard).
The most efficient photovoltaic cell was based on a nitrogen-
doped system (to enhance visible-light absorption) and gave a
photocurrent of 5.8 μA/cm2 when used with an iodide
electrolyte (which is commonly used in DSSCs).123 Later on
the popular ruthenium sensitizer cis-bis(isothiocyanato) bis-
(2,2′-bipyridyl-4,4′-dicarboxylato ruthenium(II) (N3, Scheme
8) was used for several titanium-containing zeolites and
microporous molecular sieves.562 The best results were
obtained for nanocrystalline Ti/Beta zeolite, which gives a
photocurrent of approximately 100 μA/cm2. Figure 61B shows
the working principle of such a solar cell, emphasizing the need
for electron hopping between Ti traps as a possible mechanism
for electron transport to the anode. In the same solar cell
configuration, P25 TiO2 nanoparticles (standard in DSSC
architectures) give a much higher short-circuit current density
of 4.2 mA/cm2. However, the photocurrent density corrected
by the Ti content was calculated to be similar to the value for
Ti/Beta zeolite.
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The subsequent contribution of the same group was devoted
to Ti-modified mesoporous molecular sieves.563 The material
with isolated titanium atoms forming part of a framework of
mesoporous MCM41 silica (Ti/MCM41) has a high surface
area of approximately 880 m2 g−1. In the DSSC’s configuration
with N3 sensitizer, this material results in a photocurrent
density of 45 μA/cm2. Further studies using a similar concept
were performed with the organic dye TPC1 (Scheme 4) as the
sensitizer.563 Two kinds of Ti-doped mesoporous structures
were used: titanium atoms incorporated into the previously
prepared MCM41 framework by the grafting method and small
titania nanoparticles used as one of the components in building
the hexagonal mesoporous structure of SBA15.564 Figure 62A
presents a schematic visualization of the two structures,
showing titania domains approximately of 2 nm in size in the
TiMCM41 grafted material. The dye content per Ti atom is
much better for the TiMCM41 material. Therefore, this hybrid
structure was tested in solar cells and compared with the
performance of DSSCs using standard P25 titania nano-
particles.326 As seen in Figure 62B, the photocurrent density is
low, approximately 60 μA/cm2 for 50 mW/cm2 illumination,
which is the main reason that the total sunlight conversion
efficiency of the TiMCM41 cells is approximately 2 orders of
magnitude lower than that of the cells with P25 particles. The
photocurrent per Ti atom is again comparable in both systems
(as in the previous studies with N3 dye), but the photocurrent
per loaded TPC1 dye (and, thus, per absorbed photon) is much
lower in the MCM41-based devices. The ultrafast and fast
dynamics of EI and dye regeneration are even slightly better in
the TiMCM41 cells (some details are presented in the
discussion of electron transfer, section 3.2.1.2). Therefore, the
main reason for the overall low photocurrent in TiMCM41 was
proposed to be due to slow ET to the anode. Since electrons
need to hop between titania domains in the insulating SiO2
material, the dynamics of this process might be insufficient to
compete with electron recombination to the electrolyte
(occurring on the time scale of milliseconds to seconds),
even at zero bias voltage (short-circuit conditions).
Ti-doped zeolites or MCM41 materials were also tested with
dyes that do not form covalent bonds with Ti atoms. The
emission of 7-HQ (Scheme 3) was observed to be partially
quenched in TiMCM41 material with 3% or 6% titania content
and completely quenched in a pure titania support.200 The
ultrafast dynamics in these systems are presented in section
3.2.2.2. t-St (Scheme 4) was incorporated into MOR zeolite on
which TiO2 nanoclusters were deposited, and it was observed
that the presence of titania stabilized the dye radical cation.358
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This effect is attributed to the capture of the ejected electron by
the semiconductor domains.
As mentioned above, the all-silica parts with high bandgap
prevent fast electron transport in DSSCs. From the perspective
of electron migration, materials made exclusively from TiO2 but
maintaining the mesoporous structure of a silica template could
be much more efficient. The potential advantage of this concept
is that a large crystalline titania network might transport
electrons even better than a layer of sintered titania
nanoparticles, having many trap states at grain boundaries.
An alternative nanoporous TiO2 material was prepared using a
silicate SBA15 framework as a template.565 After the growth of
the TiO2 nanostructure, the silicate component was removed
from a NaOH solution. The photocurrent of a DSSC with this
material, sensitized with ruthenium dye ditetrabutylammonium-
cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)
ruthenium(II) (N719, Scheme 8), is as high as 16.7 mA/cm2.
An analogous solar cell made with standard P25 titania particles
as a control exhibits approximately two times lower efficiency.
More recently, mesoporous TiO2 single crystals were prepared
from a framework of silica spheres, and all-solid DSSCs were
constructed entirely below 150 °C.566 The silica template was
finally removed by selective etching in aqueous NaOH to
recover the mesoporous TiO2 crystal product. This meso-
porous TiO2 gives a photocurrent higher than 6 mA/cm2 when
sensitized with the organic dye D102 (Scheme 8).
An interesting new concept for photovoltaics using zeolites,
called FRET-sensitized solar cells, was also proposed and is
illustrated in Figure 63.393 Here, light is absorbed over a broad
Figure 63. Schematic illustration of a FRET-based DSSC. The
composite consists of nanochannels containing two types of
chromophores (blue and green) and stopcocks (red). Reprinted
from ref 393. Copyright 2012 American Chemical Society.
spectral range in the dye-zeolite antenna composite. The
excitation energy migrates by radiationless transfer (FRET)
along the inserted dye in one direction (because of the specific
ordering of the dyes) and reaches the active medium to drive
the charge-separation process. The illustration in Figure 63
shows that the excited stopcock molecules (at the end of
antenna system) transfer their energy via FRET to the
semiconductor (silicon). Another version of FRET-sensitized
solar cells was proposed in conjunction with organic solar cells,
where the active medium is polymer.567 In such solar cells, the
common drawback of the active material is the limited spectral
range of high absorption of light. Zeolite-based antenna systems
can enhance light harvesting ability for photons of higher
energy than that of the active medium.
CdS and PbS QDs were encapsulated in Y zeolites and tested
in solar cell configurations.568,569 CdS-loaded zeolite Y films
grown on indium tin oxide (ITO) glass show a photovoltaic
response in an electrolyte solution consisting of Na2S and
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NaOH, giving a photocurrent density of 0.3 mA/cm2.
Electrolyte-mediated charge transport between the intercon-
nected QDs in zeolite was proposed, with electron transfer
from S2− anions in the solution to the hole in the valence band
of the CdS QDs. Interestingly, in the analogous configuration
(in the photoanode), PbS did not show any photovoltaic
response. However, it was successfully used in the counter
electrode. In this configuration with both CdS-loaded zeolite on
the photoanode and PbS loaded on the photocathode, the
overall photocurrent increased to almost 1 mA/cm2. The
proposed energetic scheme and electron transfers for this
arrangement are presented in Figure 64.
Figure 64. Diagram of the energy levels in the most efficient
configuration of quantum dots solar cell in zeolite Y. Reprinted from
ref 568. Copyright 2011 American Chemical Society.
Finally, the optoelectronic properties of metal halide
perovskite material of huge interest in photovoltaics570 have
been also recently tested in interaction with SBMs for
perovskite-based solar cells improvement. Methyl ammonium
(MA) lead halide perovskites were recently incorporated inside
mesoporous silica templates.571 The average fluorescence
lifetime decreases from hundreds of nanoseconds in the bulk
to tens of nanoseconds in the silica template. The lifetime also
decreases when the pore size was decreased from 7.1 to 3.3 nm,
accompanied by a blue shift of the perovskite emission band.
Interestingly, it was found that the confinement in the rigid
silica template protected the perovskite from various types of
degradation that occur in the bulk.570 Although such silica-
coated perovskites are not applicable in photovoltaics, they
have been proposed as useful reference materials for
comparison with other perovskites or as functional materials
in all-solid-state light-emitting diodes (see previous section on
photonics applications).
SBMs have been recently proposed as alternative meso-
porous scaffolds in perovskite solar cells. So far, the most
typical material used in this context in perovskite solar cells was
TiO2, which assists in electron transport (like in DSSCs).
However, it was shown that nanostructured materials with large
bandgap (like Al2O3) can also be used in efficient perovskite
solar cells because the electrons are easily transported to the
electrode within perovskite itself, without mediation of the
scaffolds.572 Therefore, SiO2 nanoparticles were first tested.573
Particles of different diameters (from 15 to 100 nm) were
probed, and the best results were obtained for 50 nm silica
NPs: sunlight conversion efficiency 11.45% with respect to
10.29% for the device with TiO2 scaffold layer. The lower
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Figure 65. (A) Illustration of perovskite penetration into the scaffold silica layer and its dependence on the SiO2 nanoparticles sizes. Reprinted from
ref 573. Copyright 2014 American Chemical Society. (B) Luminescence decays of MAPbI3 films of different scaffold materials. Reprinted with
permission from ref 576. Copyright 2016 Elsevier B.V.
performance of smaller silica NPs was explained in terms of not
sufficient infiltration of perovskite into the scaffold layer (Figure
65A). SiO2/TiO2 hollow nanoparticles improve the perform-
ance with respect to pure TiO2 ones due to higher
photovoltage.574 The highest efficiency is 14.7% for MAPbI3
perovskite and Al doping in the ET layer. Silica nanorods with
controlled aspect ratios were then used as scaffold layers.575
The highest conversion efficiency (13.9%) was obtained for
relatively long SiO2 nanorods with an aspect ratio of 5. In
comparison to nanospheres of 80 nm diameter, nanorods
provide better perovskite infiltration. Even higher efficiency
(16.2%) was achieved for commercial SiO2 nanoparticles
(Degussa, A200).576 This system is better than those with
mesoporous TiO2 or Al2O3 scaffolds due to better photovoltage
and fill factor of the cells. Moreover, hysteresis for SiO2-based
perovskite solar cell is also less severe, and the luminescence
decay is the longest for silica layers (Figure 65B).
SBMs were also tested in planar perovskite cells. Using silica-
coated gold nanorods improves the efficiency from 15.6% to
17.6%.577 The effect is attributed to localized surface plasmon
resonance of gold (section 3.3.4). Not only increased incident
light trapping (higher photocurrent) but also improved
transport and collection of charge carriers (better fill factor)
is observed in the devices with silica-coated gold nanorods.
Similar efficiency enhancement (from 15.85% to 17.6%) was
reported upon adding hexagonal mesoporous silica islands to
planar junction perovskite solar cells.578 Instead of forming a
continuous scaffold layer, wormholelike hexagonal mesoporous
silica form random islands on top of a compact TiO2 blocking
layer. This improvement is due to increased light trapping effect
and pinhole-blocking effect.
5.4. Drug Delivery
Drug delivery is a process in which several fundamental fields of
modern science converge.579 With the development of new and
advanced nanocarriers, it is at the frontier of nanotechnology
and material chemistry and its underlying goal of bringing
therapeutic or imaging agents to the desired site is related to
biology and medicine.579,580 The delivery process can be
considered a succession of several steps: loading, delivery,
targeting, and release. The medical applications of nano-
technologies have propelled the development of various types
of drug-loaded nanocarriers, such as liposomes, cyclodextrins,
micelles, polymers, and metal−organic framework
(MOFs).579,581−586 In the ideal case, nanoparticle-based
delivery systems are expected to accumulate in the required
organ or tissue and simultaneously penetrate target cells to
deliver the bioactive agent. Any smart drug delivery system
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should be multifunctional and should possess the ability to on
demand switch on and off certain functions.587−589 Due to their
versatile properties for drug delivery, including biocompati-
bility, high pore volume, tunable pore size, and versatile
chemistry for surface functionalization, mesoporous silica
nanoparticles (MSNs) are an attractive system for the
development of drug delivery nanocarriers. The high pore
volume and the ability to tune the pore size allow high drug
loading of both small-molecule drugs and large biomacromo-
lecules.25,590 Furthermore, the surfaces of these nanoparticles
can be easily functionalized to allow the pores to be gated by
molecules that are responsive to external stimuli (e.g., light,
heat, pH, redox, and magnetic fields, to name just a few
examples), most notably pH changes and light irradia-
tion.25,590−592 To develop such systems, a great detailed
knowledge of their behavior upon cell internalization and
during the triggered release is needed.
A number of mesoporous silica drug delivery systems has
been developed to realize controllable drug release by
employing different kinds of pH- and redox-sensitive pore
capping architectures that can be switched on to release drug
molecules from the mesoporous structure.25,590,592−596 In many
cases, the extracellular environment around solid tumors
becomes acidic as a result of the Warburg effect, associated
with the increased production of lactate by the cancer cells, thus
allowing for selective and targeted drug release.597 A recent
example is the introduction of a targeting polymer, poly-
(ethylene glycol)−folic acid (PEG−FA), on the surface of
polydopamine (PDA)-modified MSNs.598 These nanoparticles
were employed as a drug delivery system loaded with
doxorubicin (DOX, Scheme 8). In this system, the pH-sensitive
PDA coating serves as a gatekeeper. In vitro release
experiments have shown pH-dependent, sustained drugs release
profiles that could enhance the therapeutic anticancer effect and
minimize the potential damage to normal cells. Furthermore,
the nanoparticles achieved significantly high targeting efficiency,
as demonstrated by the in vitro cellular uptake and cellular
targeting assays.598 An MSN functionalized with disulfide snap-
tops has been developed showing high drug loading and
selective intracellular drug release in response to the redox
potential.599 These nanoparticles, when loaded with a Hoechst
fluorescent dye, release their cargo exclusively intracellularly
and stain the nuclei of macrophages. The particles loaded with
moxifloxacin kill F. tularensis in macrophages in a dose-
dependent manner. In a different strategy, silylated precursors
with molecular recognition sites based on triazine and uracil
fragments were grafted onto MSN surfaces.600 After loading
with cargo molecules (dyes or drugs), the nanoparticles were
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Figure 66. (A) Schematic presentation of the synthesis concept and drug release of Pt@PAA-MSNDOX. In vitro (B) Pt(II) and (C) DOX release
behaviors of Pt@PAA-MSNDOX in aqueous solutions with and without 0.9% NaCl at pH 7.4 and 5.5, respectively. Reprinted with permission from
ref 601. Copyright 2016 Royal Society of Chemistry.
successfully capped by H-bonding to the complementary caps,
which were prepared by covalently coupling a uracil or adenine
unit to the bulky β-CD. The pH sensitivity of these systems was
demonstrated by the release of dye molecules (propidium
iodide or RhB) at acidic pH. The particles were stable at neutral
pH, showing no premature release and a controlled release
triggered by an acid stimulus. Cytotoxicity experiments on
human breast cancer cells using nanoparticles loaded with
camptothecin (CPT, Scheme 8) showed a decrease in cell
viability similar to that induced by the drug alone, confirming
the release of the active compound after pore opening in the
acidic lysosomes. A much smaller amount of the chemo-
therapeutic agent CPT (40 times less) than that of the free
drug was loaded into these nanoparticles.600 A dual drug
codelivery system based on poly(acrylic acid)-modified MSNs
for the combination of DOX and cisplatin was also
demonstrated (Figure 66).601 The cisplatin was conjugated
with carboxyl groups to form pH-responsive cross-linking shells
after the encapsulation of DOX in the mesopores of the silica
particle. As a result of the pH-sensitive drug release, 70% of the
cisplatin and 80% of the DOX are released at pH 5.5, while only
16% of the cisplatin and 25% of the DOX are released at pH
7.4.601
In a different approach, a novel enzyme-based cap system
that is directly combined with a targeting ligand via bio-
orthogonal click chemistry was developed for MSNs.602 This
capping system is based on the pH-responsive binding of an
arylsulfonamide-functionalized MSN and the enzyme carbonic
anhydrase (CA). An unnatural amino acid (UAA) containing a
norbornene moiety was genetically incorporated into CA,
allowing the site-specific bio-orthogonal attachment of very
sensitive targeting ligands such as folic acid and anandamide.
This specific attachment leads to specific receptor-mediated cell
and stem cell uptake. The study reported the successful delivery
and release of the chemotherapeutic agent actinomycin D to
Kleihauer-Betke (KB) cells.602
MSNs can also be functionalized so that their pores are gated
by light-responsive molecules.603,604 Several strategies have
been proposed and realized for light-activated cargo release
from these materials.603,605,606 The initial strategy was based on
the use of a UV−visible light. Bis(clickable) mesoporous silica
nanospheres (ca. 100 nm) were obtained by the co-
condensation of TEOS with variable amounts of two clickable
organosilanes (2−5% each) in the presence of CTAB.607 These
nanoparticles could be functionalized easily with two
independent functions using copper-catalyzed alkyne−azide
cycloaddition (CuAAC) to transform them into nanocarriers
bearing cancer cell targeting ligands with the ability to deliver
drugs on demand. Active targeting was made possible by
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anchoring folic acid by the CuAAC click reaction, whereas
controlled delivery was performed by clicked azobenzene
fragments.607 The azobenzene groups can obstruct the pores of
the nanoparticles in the dark, whereas upon irradiation by the
UV or blue light, their trans-to-cis photoisomerization induces
disorder in the pores, enabling the delivery of the cargo
molecules. The on-command delivery was proven in solution
by dye release experiments and in vitro by DOX delivery.607
The added value of the folic acid ligand was clearly evidenced
by the difference in cell killing induced by doxorubicin-loaded
nanoparticles under blue irradiation depending on whether the
particles featured the clicked folic acid ligand or not. However,
UV light activation is not easily applicable for biology, since
one-photon irradiation has limited tissue penetration, may
induce phototoxicity, and lacks spatial accuracy. To overcome
this limitation, recent studies have reported on the use of NIR
two-photon-triggered drug release.608−610 To date, a variety of
NIR light-responsive drug delivery systems based on different
mechanisms have been developed for controllable drug
delivery.610 The photothermal effect, which normally utilizes
red or NIR-absorbing agents to generate heat from NIR optical
energy, may be employed to trigger drug release from
photothermal-responsive drug delivery systems.610−612 Upcon-
version nanoparticles, which can be excited by multiple NIR
photons and emit a single high-energy photon with a shorter
wavelength, even in the UV region, have also been used for
NIR light-responsive drug release.613 MSNs functionalized with
azobenzene and containing a two-photon fluorophore demon-
strated the triggered release of cargo molecules.614−616 The
release was achieved by NIR light irradiation because the two-
photon fluorophore emit 420 nm light, which matches the
azobenzene absorption band, leading to successful isomer-
ization of the azobenzene gates.616 Two-photon-sensitive
mesoporous organosilica nanocarriers (M2PS) were synthe-
sized via the co-condensation of a silica precursor and a two-
photon electron donor (2PS).612 First, one- and two-photon-
actuated cargo (DOX) release via the photoreductive cleavage
of the disulfide nanogates of the MSN using M2PS-35 and
M2PS-16 was successfully monitored in aqueous solutions.
Furthermore, the cellular uptake in Michigan Cancer
Foundation 7 (MCF-7) cells was demonstrated via two-photon
fluorescence imaging of the nanoparticles, which were then
applied successfully for drug delivery in cells (Figure 67).612
Spatially confined cyanine-anchored silica nanochannels
loaded with chemotherapeutic DOX were synthesized for
light-driven synergistic cancer therapy.617 The cyanine dye is
present within the nanochannels in a J-type aggregation
conformation, and DOX is encapsulated via π−π interactions
with the cyanine dye. Under NIR light irradiation, the loaded
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Figure 67. Images of (A) M2PS-35 and (B) M2PS-16 using two-
photon fluorescence showing the cellular uptake of the nanoparticles
(Scale bar 10 mm). (C) Two-photon triggered DOX delivery using
M2PS-35 and M2PS-16 silica-based gates. Reprinted from ref 612.
Copyright 2015 American Chemical Society.
particles exhibit enhanced photothermal conversion efficiency
due to the maximized nonradiative transition of the J-type
aggregates. These trigger light-driven drug release through the
destabilization of temperature-sensitive π−π interaction and
cause the effective intracellular translocation of DOX from the
lysosomes to the cytoplasm via reactive oxygen species-
mediated lysosomal disruption, thereby causing potent in vivo
hyperthermia and intracellular trafficking of the drug into the
cytoplasm at tumor sites.617 A red light (660 nm)-responsive
drug delivery system based on cyclodextrin (CD)-gated MSNs
containing a photodynamic therapy (PDT) photosensitizer Ce6
(Scheme 5) was reported.618 In water, Ce6 can be excited by
red light to generate singlet oxygen, which can further cleave
the sensitive linker to trigger the departure of CD and the
release of cargo. In vitro release experiments have shown the
cargo to be released from MSNs by irradiation with red light
and then to spread into the entire cell. The relatively low power
density (0.5 W cm−2) of the excitation light together with the
short irradiation time (1−3 min) result in a low light dose (30−
90 J cm−2) for the drug delivery.618 A novel light-responsive
drug delivery platform based on Ce6-doped mesoporous silica
nanorods (CMSNRs) was developed for on-demand light-
triggered drug release.619 In one such architecture, the
nanorods are coated with bovine serum albumin (BSA) protein
via a singlet oxygen sensitive bis(alkylthio)alkene (BATA,
Scheme 8) linker and then modified with polyethylene glycol
(PEG).619 The obtained CMSNR-BATA-BSA-PEG, termed
CMSNR-B-PEG, acts as a drug delivery carrier loaded with
either small drug molecules such as DOX or larger macro-
molecules such as cisplatin predrug-conjugated third-generation
dendrimer (G3-Pt), both of which are sealed inside the
mesoporous structure of the nanorods by BSA coating. Upon
660 nm light irradiation with a relatively low power density,
CMSNRs with intrinsic Ce6 doping generate singlet oxygen to
cleave the BATA linker, inducing the detachment of BSA-PEG
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from the nanorod surface and thus triggering the release of the
loaded DOX or G3-Pt. As evidenced by both in vitro and in
vivo experiments, CMSNR-B-PEG with either DOX or G3-Pt
loading offers remarkable synergistic therapeutic effects in
cancer treatment owing to the on-demand release of
therapeutics specifically in the tumor under light irradiation.619
Ce6-gold composites in mesoporous silica shell for drug release
were also studied,417 and they were shortly presented in section
3.3.4.
The combination of pH and light as external stimuli has also
been reported. MSNs have been synthesized and loaded with
both aluminum chloride phthalocyanine (AlClPc) and cisplatin
as combinatorial therapeutics for treating cancer.620 The
intracellular uptake and cytotoxicity were evaluated in human
cervical cancer (HeLa) cells by confocal laser scanning
microscopy (CLSM) and 3-(4,5-dimethylthiazol-2-yl)-5-(3-
carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium
(MTS, Scheme 8) assays, respectively, showing that the
mesoporous materials can be readily internalized by HeLa
cells.620 The cytotoxicity experiments demonstrated that after
light exposure, the combination of AlClPc and cisplatin
compounds in the same platform potentiates the toxic effect
against HeLa cells in comparison to the effects of the control
AlClPc-MSN and cisplatin-MSN materials.620 A similar
approach has been applied to the synthesis of a dual pH-
responsive MSN-based drug delivery system for synergistic
chemo-photodynamic therapy.621 By grafting histidine onto the
silica surface, acid-sensitive PEGylated tetraphenylporphyrin
zinc (Zn-Por-CA-PEG) was used as a gatekeeper to block the
nanopores of the particles via the metallo-supramolecular-
coordinated interaction between Zn-Por and histidine. This
gatekeeper is stable enough to prevent the loaded drug from
leaching out in healthy tissue. However, at the extracellular pH
of cancer, the conjugated acid-sensitive cis-aconitic anhydride
between Zn-Por and PEG is cleaved, and the surface of Zn-Por
becomes positively charged to facilitate cell internalization.621
Due to the removal of the gatekeeper, the metallo-supra-
molecular-coordination disassembles in intracellular acidic
microenvironments to release the carried drug and Zn-Por.
The photosensitivity of Zn-Por further enables the combination
of chemotherapy and photodynamic therapy.621 The idea of
dual-stimulus synergy has been further expanded to a new
nanocomposite using reduced graphene oxide (rGO) and
mesoporous silica−DOX/hydroxyapatite (HA).622 Owing to
the relatively high loading capacity of the anticancer drug DOX,
the biomimetic capping of nontoxic and pH-dependent
biodegradable HA on the surface of the composite and the
efficient photothermal conversion effect of rGO under NIR
irradiation, the nanocomposite provides a pH−light dual-
triggered drug release. The in vitro experimental results have
indicated that the chemotherapeutic effect of DOX and the
hyperthermia induced by rGO under NIR light irradiation kill
HeLa cells effectively.622
Finally, mesoporous SBMs can be used both as drug
nanocarriers and as “reactors” for the noncovalent assembly
of synergetic entities (Figure 68). The first such example of
noncovalent assembly between FA and a porphyrin [tetrakis(4-
carboxyphenyl)porphyrin, TCPP] in mesoporous silica par-
ticles has been reported recently.623 The assembly process does
not occur in aqueous solutions but occurs exclusively in the
interior of the mesoporous silica material that entraps both
components. The assembly shows enhanced and preserved
fluorescence in the FA and TCPP spectral regions, respectively,
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Figure 68. Schematic representation showing the concept of PDT
using FA/TCPP assembly released from mesoporous silica material to
kill cancer cells. Reprinted with permission from ref 623. Copyright
2017 Wiley-VCH.
along with the ability to photosensitize the formation of singlet
oxygen slightly better than the free photosystem can. The
assembly has demonstrated high potential for the photo-
inactivation of KB cancer cells over expressing the folate
receptors, compared with the potential of free TCPP, most
likely because of the FA targeting effect.623
In this part, we highlighted the versatility of SBMs for the
development of various and diverse applications. The specific
features of SBMs, such as high surface area, high thermal and
mechanical stability, good and selective adsorption capacity,
and the presence of active sites make these materials one of the
most used in the field of catalysis (section 5.1). The design of
new sensors (section 5.2) and their encapsulation leading to the
formation of composites of high photostability and brightness is
another field under development. The use of these systems
allows development of smart sensor devices. Light collection
and transmission, which can be realized using 1D oriented
hosts (most often zeolite L) with properly designed
chromophores inside, acting as antenna-like systems, is another
field of nanophotonics (section 5.2). Increased interest has
been recently shown to new sources of light based on SBMs. In
dye-sensitized solar cells, micro- and mesoporous silica
materials have been used instead of semiconducting titania
nanoparticles (Section 5.3). Silica-coated gold nanostructures
have been tested to enhance the light absorption by the active
layer of solar cells. Mesoporous silica scaffolds in perovskite
solar cells are perhaps the most successful use of these materials
in photovoltaics so far, playing a totally passive role (electrons
are transported via perovskite material, unlike the typical
architectures with titania layers). Finally, mesoporous SBMs
represent an attractive alternative to the conventional drug
delivery systems (section 5.4). The controlled release offered
by these materials has many advantages such as high release
efficiency, precise control of the dosage form for prolonged
periods, and decreased toxicity. Surface modifications open new
possibilities for controlled drug release and targeting drug
delivery. In this section, two of the more investigated
approaches (light and pH) for external stimuli-responsive
drug delivery have been reviewed.
6. GENERAL CONCLUSION AND OUTLOOK
In this review, we have commented on and discussed the
confinement effect of SBMs on the spectroscopy and dynamics
of guests, ranging from classical organic dyes to drug molecules
and quantum dots. The basic concepts of confining molecules
to change their photobehavior and related molecular state
BJ
Review
(monomers or aggregates) is demonstrated in hundreds of
reports using time- and space-resolved laser-based techniques.
Not of less importance, theoretical approaches have been
applied to explore solvation and guest interaction with the
SBMs. Due to the related composites complexity and large
number of atoms (host + guest + solvent) to consider, the
available theoretical tools are not as sophisticated. However,
relevant information on the composites and nanosolvation
could be extracted, suggesting new experiments. We have
further reviewed the development of different applications
associated mainly with the use of light to trigger the desired
process in these composites. These applications include
photocatalysis, nanosensors, photonics, photovoltaics, and
drug delivery systems, demonstrating the versatility and
significance of these materials for modern science and
technologies. Clearly, thanks to the advancements in ultrafast
and single-molecule spectroscopic techniques, computational
methods, and theoretical models, the understanding of many
photophysical processes in SBMs, such as solvation dynamics,
proton, electron, and energy transfer has increased in the past
decade. The reviewed works have provided a wealth of
paramount information on the excited-state behavior of organic
molecules and metal complexes interacting with SBMs, in
particular, depicting photoinduced dynamic processes as
mechanistically different from those in homogeneous solutions.
Yet, a certain discrepancy exists between the theoretical and
experimental works. On one hand, the details of the predictions
of models for solvation or vibrational correlation require
experimental verifications. On the other hand, the complex
systems investigated experimentally for the possible applica-
tions are usually still too complicated for the current calculation
resources and methods. Developing more precise theoretical
treatments that describe complex kinetic behavior of excited
species within SBMs are very important to get a picture at
atomic and orbital levels. Nevertheless, the combination of the
theoretical and experimental approaches has helped to clarify
the SBMs considerably from the photodynamical point of view.
The ultrafast spectroscopic techniques still have experimental
limitations and technical issues, related to the nature of the
samples, which are in suspensions or solids, and are highly
heterogeneous, to be overcome for providing high quality
experimental data. Technological advances should allow for the
development of more sensitive techniques with better time and
spectral and spatial resolution that can monitor weakly bonded
guest-SBMs. This in turn will open the possibility to better
characterize the molecular interaction in SBM complexes with
application in photonics, catalysis, sensors, or drug delivery.
From the applications point of view, the meso- and
microporous SBMs have a unique set of properties, such as
high surface area, high thermal and mechanical stability, good
and selective adsorption capacity, presence of active sites, and
ability for surface modifications. These features are paramount
for the development of a variety of new smart devices with
applications in a broad range of technologies. With the
improvement of our fundamental knowledge of photoinduced
processes within the related composites, we should be able to
address further challenges in related fields, such as selective
control and better yield of photoinduced reaction (photo-
catalysis), better sensitivity and selectivity (sensors), more
efficient light absorbing and converting devices (photonics), or
improved targeting and selectivity to enhance cellular/tissue
recognition to specifically match only the receptors present in
diseased cells (drug delivery). Overcoming these challenges will
DOI: 10.1021/acs.chemrev.7b00422
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Chemical Reviews
open new avenues in the SBMs science and technology. For
example, limited brightness and photostability of many probes
are one of the major constraints in using them in sensing in
chemical and biological systems. Overcoming this limitation by
trapping into or bonding them to SBMs would allow for
improved spatial resolution in confinement and tracking studies
getting higher performence imaging for better understanding
and smarter design. Such composites with well-defined sizes,
surface hydrophobocity/hydrophilicity, sensitivity to changes in
the local environment, and having strongly polarized emission
would also be useful for probing the accessible internal
dimensions of confining nanostructures, including canals of
biological moecules. Advanced ultrafast vibrational, electronic
and X-ray spectroscopy, and 4D electron microscopy are some
of the modern tools to explore the intimate interactions in the
formed composites at atomic and short-time scales.624−635 With
these powerful techniques, one can explore for example the
time evolution of the electric field effect generated by the
doping metal in the framework on the composite robustness
and performance. While with the current knowledge on
photophysics and photochemistry one can predict the photo-
behavior of a given molecule in solution when the properties of
the solvent are known, we hope that, in the near future, similar
understanding related to SBMs will come, knowing the basic
properties of silica material (morphology, size, doping, etc.) will
enable one to foresee the photoresponse of a given
encapsulated organic or inorganic guest in the composite.
AUTHOR INFORMATION
Corresponding Author
*E-mail: abderrazzak.douhal@uclm.es. Tel: +34 925 265717.
ORCID
Marcin Ziółek: 0000-0003-1882-6022
Abderrazzak Douhal: 0000-0003-2247-7566
Notes
The authors declare no competing financial interest.
Biographies
Noemi ́ Alarcos studied chemistry at the University of Castilla-La
Mancha (UCLM, Spain) and obtained her diploma in 2010. She
obtained (2015) her Master’s and Ph.D. diplomas in (Physical)
Chemistry from the UCLM under the supervision of Prof.
Abderrazzak Douhal. Since 2015, she is continuing her research as a
postdoctoral student in the same group thanks to a CYTEMA grant.
Her main research interest is focused on the fast and ultrafast
dynamics of photoinduced processes of dyes and drugs in solutions
and within silica-based materials. ORCID: orcid.org/0000-0003-1350-
9036.
Boiko Cohen studied chemistry at the Sofia University, Bulgaria, and
obtained his diploma in 1997. He obtained his Ph.D. (2003) from the
Tel Aviv University. After postdoctoral research at the Ohio State
University and Northwestern University, he joined University of
Castilla−La Mancha in 2007 as Ramon y Cajal Fellow. He has been an
Associate Professor at the University of Castilla−La Mancha since
2012. His main research interest is the fast and ultrafast dynamics of
photoinduced processes in solution and in confining chemical and
biological media. (ResearcherID: C-4381-2008; ORCID: orcid.org/
0000-0002-5400-4678).
Marcin Ziółek is currently an Associate Professor at the Faculty of
Physics, Adam Mickiewicz University (AMU) in Poznań, Poland. His
first scientific topics were femtosecond pump−probe spectroscopy,
BK
Review
ultrashort pulse propagation, and supercontinuum generation. After
completing his Ph.D. degree (in 2003 at AMU), he started to study
excited state proton transfer process and photochromism phenomena.
From 2009 to 2011, he was a postdoc in the group of Prof.
Abderrazzak Douhal at Universidad de Castilla La Mancha in Toledo,
Spain, under the Marie Curie Fellowship. He investigated photo-
chromic molecules and dyes for solar cells encapsulated in zeolites and
mesoporous silica sieves. In 2013, he completed his habilitation degree
at AMU. His current scientific interest are dye-sensitized and
perovskite solar cells, especially studied by time-resolved laser
spectroscopy techniques. (ResearcherID: J-6666-2012; ORCID:
orcid.org/0000-0003-1882-6022).
Abderrazzak Douhal (https://www.uclm.es/profesorado/adouhal/
douhal.htm), graduated (1982) from the Faculty of Sciences at Kadi
Ayyad University (KAU, Marrakech, Morocco) and is a Professor of
physical chemistry at the University of Castilla La Mancha (1993,
UCLM, Toledo, Spain). He has received his Ph.D. degree in chemistry
from KAU after a research period at the Institute of Physical
Chemistry “ROCASOLANO” at “Consejo Superior de Investigaciones
́
Cientifica, CSIC”, Madrid. During 1990−1992, he was a postdoctoral
student (MONBUSHO and JSPS fellow, Japan) at the Institute for
Molecular Science (Okazaki, Japan). In 1993, he worked as a research-
associate at “Laboratoire de Photophysique Moléculaire, LPPM”
(University of Paris-Sud/CNRS, France). He was a visiting researcher
at California Institute of Technology (Caltech) for several periods
from 1995−2000, collaborating with Prof. Ahmed H. Zewail. Since
1998, he is heading the Femtoscience and Microscopy research group
at the UCLM, focusing his research on the study of photoevents in
condensed phase and advanced materials (silica-based materials,
MOFs, COFs, HOFs, and perovskites). ResearcherID: L-4940-2014;
ORCID: 0000-0003-2247-7566.
ACKNOWLEDGMENTS
This work was supported by the MINECO (MAT2014-57646-
P, Consolider Ingenio 2010: CSD2009-0050 MULTICAT, and
CEI CYTEMA: CEI15-08-5), JCCM (PEII-2014-003-P), and
NCN (National Science Centre, Poland, 2015/18/E/ST4/
00196). N.A. thanks the CYTEMA program for the
postdoctoral grant. We thank Dr. M. R. Di Nunzio for her
help in drawing the chemical molecular structures.
DEDICATION
This work is dedicated to the Memory of Ahmed H. Zewail.
ABBREVIATIONS
General Abbreviations
SBMs silica-based materials
ICT intramolecular charge transfer
TICT twisted-intramolecular charge transfer
FRET Förster (fluorescence) resonance energy transfer
2D-IR two-dimensional infrared spectroscopy
DFT density functional theory
TD-DFT time-dependent density functional theory
MOs molecular orbitals
HOMO highest occupied molecular orbital
LUMO lowest unoccupied molecular orbital
HOC hydrophobic cavities
HIC hydrophilic cavities
RHOC rugged pores of the hydrophobic cavities
PT proton transfer
ESPT excited-state proton transfer
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Chemical Reviews Review

GSPT ground-state proton transfer k1, k2 (k‑1, k‑2) forward (reverse) proton-transfer rate con-
ESIPT excited-state intramolecular proton transfer stants
GSIPT ground-state intramolecular proton transfer τ fluorescence lifetime
UV ultraviolet α heterogeneity parameter
NIR near-infrared region D donor
SCK Smoluchowski-Collins-Kimball A acceptor
PES potential energy surface λ reorganization energy
IHB intramolecular H-bond d diameter
KIE kinetic isotopic effect M+ metal cation
IVR intramolecular vibrational-energy redistribution kb back electron transfer rate constant
VR vibrational relaxation R0 Förster distance
Me methyl kEnT energy-transfer rate constant
BET Brunauer-Emmet-Teller ksv Stern−Volmer quenching constant
CT charge transfer r distance
ET electron transfer μm micrometer
CS charge-separated P polarization
LE locally excited w/w % percent of weight per weight
PZC point of zero charge Ln lanthanides
EI electron injection
LED light-emitting diode
CB conduction band Material Structures
ICS intersystem crossing LTA Linde type A zeolites
EPR electron spin resonance LTL Linde type L zeolites
CR charge recombination H-LTL acidic LTL zeolites
HT hole transfer K-LTL potassium LTL zeolites
I⊥/I∥ depolarization ratio CD cyclodextrin
QDs quantum dots MCM41 (MCM48) Mobil Catalytic Materials of number 41
EnT energy transfer process (48)
Homo-EnT homo-energy transfer SBA15 Santa Barbara Amorphous type material
SET surface energy transfer HSA human serum albumin
p6mm 2D-hexagonal symmetry FAU Faujasite
sSMT spectroscopic single-molecule tracking MFI mordenite framework inverted
FCS fluorescence correlation spectroscopy FER ferrierite zeolites
fwhm full width at half maximum MOR mordenite zeolites
ZVIP zero valent iron particles P25 titania nanoparticles
TOC total organic carbon TiMeso crystalline mesoporous all-TiO2 structure
STEM scanning transmission electron microscopy ZSM-5 zeolite Socony Mobil-5
CIE Commission Internationale de l’Éclairage AlPO4 aluminophosphate
DSSCs dye-sensitized solar cells CTAB micelles cetyltrimethylammonium bromide mi-
PDT photodynamic therapy celles
CLSM confocal laser scanning microscopy Cal-NAM calcined-nanochannel-incorporated alu-
rGO reduced graphene oxide mina membrane
TMS-NAM trimethylsilyl-nanochannel-incorporated
Symbols and Rate Constants alumina membrane
Å Ångstrom RWY chalcogenide-based zeolite
nm nanometer PMO periodic mesoporous organosilica
ε dielectric constant Bp-PMO biphenylylene-bridged periodic mesopo-
E, E* enol, photoexcited enol rous organosilica
K, K* keto, photoexcited keto Au NPs gold nanoparticles
AN, AN* anion, photoexcited anion APO aluminophosphate
Z, Z* zwitterion, photoexcited zwitterion Lap laponite
N, N* neutral, photoexcited neutral form MCM41-SHNFs thiol-functionalized MCM41 nanofibers
T, T* tautomer, photoexcited tautomer GBZ graphene-Bi8La10O27-zeolite
S1 electronically first excited state APbX3 general perovskite formula
S0 ground-electronic singlet state MSNs mesoporous silica nanoparticles
kPT deprotonation rate constant M2PS mesoporous organosilica nanocarriers
krec recombination rate constant synthesized via the co-condensation of a
kD (k‑D) forward (reverse) diffusion-controlled rate silica precursor and a two-photon elec-
constant tron donor
ms millisecond HMSNs hollow mesoporous silica nanoparticles
ns nanosecond MOFs metal−organic frameworks
ps picosecond CMSNRs Ce6-doped mesoporous silica nanorods
fs femtosecond BSA bovine serum albumin protein
BL DOI: 10.1021/acs.chemrev.7b00422
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Chemical Reviews Review

AOT aerosol-OT [sodium bis(2-ethylhexyl) LDQ 1-[4-(4′-methyl)-2,2′-bipyridyl]-2-[4-(4′-

sulfosuccinate] N,N′-tetramethylene-2,2′-bipyridinium)]-
EMT hexagonal analog faujasite type zeolite ethene
MSUH hexagonal ordered 1D-channels meso- NB Nile blue
phase MB Methylene Blue
MCF-7 Michigan Cancer Foundation 7 Py+ pyronine
ITO indium tin oxide PyB+ pyronine B
HeLa human cervical cancer cells PyY+ pyronine Y
KB Kleinhauer-Betke cells AP aminopropyl
AO acridine orange
Molecules RhB rhodamine B
TNT trinitrotoluene Rh3B rhodamine 3B
FL fluorenone PFH+ proflavine ions
OX+ oxinine R6G rhodamine 6G
Ibu ibuprofen PBI perylene bisimide
TRITC tetramethylrhodamine isothiocyanate PTP p-terphenyl
DEAC 7-diethylaminocoumarin-3-carboxylic acid TPPy tetraphenylpyrene
butylamine ester Bp biphenylylene
CAN canthaxanthin C1 coumarin 1
MeAcr+ methylacridine PDI N,N′-bis(2,6-dimethylphenyl)-3,4,9,10-pery-
PIC cyanine (1,1′-diethyl-2-2′-cyanine iodine) lenediimide
AF acriflavine hydrochloride NI 1,8-naphthalimide
Th+ thionine DOC 3,3′-diethyloxacarbocyanine
C153 coumarin 153 SY super yellow
2-NpOH 2-naphthol IRIS3 cyanine dye
HPTS 8-hydroxypyrene-1,3,6-sulfonate (pyranine) C30 coumarin 30
6-HQ 6-hydroxyquinoline DXP N,N′-bis(2,6-dimethylphenyl)-3,4,9,10-pery-
7-HQ 7-hydroxyquinoline lenetetracarboxylic diimide
AcOH acetic acid PR149 N,N′-bis(3,5-dimethylphenyl)-3,4,9,10-pery-
HBT 2-(2′-hydroxyphenyl)benzothiazole lenetetracarboxylic diimide
HBO 2-(2′-hydroxyphenyl)benzoxazole HPDI N,N′-bis(1-hexylheptyl)-3,4,9,10-perylenete-
HBTNH2 2-[5′-N-(3-triethoxysilyl)propylurea-2′- tracarboxylic diimide
hydroxyphenyl]benzothiazole SAs salicylideneanilines
PF proflavine C-SNARF-1 (5′ and 6′)-carboxy-10-(dimethylamino)-3-
BZP benzophenone hy dr oxy s pir o[7H-b enz o[c ]xanthene-
HYZ hydrazone 7,1′(3H)-isobenzofuran]-3′-one
SAA salicylaldehyde azine FFA furfuryl alcohol
HBA-4NP (E)-2-(2′-hydroxybenzyliden)amino-4-nitro- DY-630-MI (E)-2-((E)-3-(2-(tert-butyl)-7-(diethylami-
phenol no)- 4a,8a-dihydrochromenylium-4-yl)-
3-HF 3-hydroxyflavone allylidene)-1-(6-((2-(2,5-dioxo-2,5- dihydro-
C339 coumarin 339 1H-pyrrol-1-yl)ethyl)amino)-6-oxohexyl)-
C340 coumarin 340 3,3-dimethylindoline-5-sulfonate
C343 coumarin 343 TC tetracycline
C480 coumarin 480 TXB Texbrite
PAC343 propylamide coumarin 343 PNT p-nitrotoluene
4AP 4-aminophthalimide CdS cadmium sulfide
NR Nile red DCF Diclofenac
TPC1 triphenylamine dye TSA tungstosilicic acid
YD2-o-C8 zinc-porphyrin MeO methyl orange
MPc metal phthalocyanine (Ru(bpy)3)+2 ruthenium tris-bipyridyl
CoPc cobalt phthalocyanine PMMA poly(methyl methacrylate)
PdPc palladium phthalocyanine MA methylammonium
MO-PdPc covalent bonding palladium phthalocyanine FA formamidinium
Acr+-Mes 9-mesityl-10-methylacridinium ion FITC fluorescein isothiocyanate
DPH 1,6-diphenyl-1,3,5-hexatriene RITC rhodamine B isothiocyanate
t-Ab trans-azobenzene Ru(Bphen)2PIP ruthenium(II) complex with Bphen = 4,7-
t-St trans-stilbene diphenyl-1,10-phenanthroline and PIP = 2-
An anethole phenyl-1H-imidazo[4,5-f ] [1,10]-
DCB 1,4-dicyanobenzene phenanthroline
PHNS phenosafranine BTPN naphthalene-bridged silane
(Ni(bpy)3)2+ tris(2,2′-bipyridine)nickel(II) DNT 2,4-dinitrotoluene
(Ru(bpy)32+ tris(2,2′-bipyridine)ruthenium(II) En ethylenediamine
MV methylviologen Tb(acacn) terbium-acetylacetone

BM DOI: 10.1021/acs.chemrev.7b00422
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