Review

pubs.acs.org/CR

Tetrathiafulvalene- (TTF‑) Derived Oligopyrrolic Macrocycles

Atanu Jana,†,‡ Masatoshi Ishida,§ Jung Su Park,∥ Steffen Baḧ ring,⊥ Jan O. Jeppesen,*,⊥
and Jonathan L. Sessler*,‡,#
†
Department of Chemistry, University of Sheffield, Sheffield S10 2TN, United Kingdom
§
Department of Chemistry and Biochemistry, Graduate School of Engineering and Center for Molecular Systems, Kyushu University,
Fukuoka 819-0395, Japan
∥
Department of Chemistry, Sookmyung Womens’s University, Seoul 140-742, South Korea
⊥
Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Campusvej 55, 5230, Odense M, Denmark
#
Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United States
‡
Institute for Supramolecular Chemistry and Catalysis, Shanghai University, Shanghai, 200444, China

ABSTRACT: After the epochal discovery of the “organic metal”, namely, tetrathiafulva-
lene (TTF)−7,7,8,8-tetracyano-p-quinodimethane (TCNQ) dyad in 1973, scientists have
made efforts to derivatize TTF for constructing various supramolecular architectures to
control the charge-transfer processes by adjusting the donor−acceptor strength of the
dyads for numerous applications. The interesting inherent electronic donor properties of
TTFs control the overall electrochemical properties of the supramolecular structures,
leading to the construction of highly efficient optoelectronic materials, photovoltaic solar
cells, organic field-effect transistors, and optical sensors. Modified TTF structures thus
constitute promising candidates for the development of so-called “functional materials” that
could see use in modern technological applications. The versatility of the TTF unit and the
pioneering synthetic strategies that have been developed over the past few decades provide
opportunities to tune the architecture and function for specific purposes. This review
covers the “state of the art” associated with TTF-annulated oligopyrrolic macrocyclic
compounds. Points of emphasis include synthesis, properties, and potential applications.

CONTENTS 2.2.1. “Pacman”-Type Schiff-Base TTF-Calix[4]-

pyrrole 2663
1. Introduction 2642 2.2.2. TTF-Annulated Calix[2]pyrrole[2]-
2. TTF-Annulated Oligopyrrolic Macrocyclic Com- thiophene 2664
pounds 2646 2.3. TTF-Annulated Expanded Calix[n]pyrroles 2664
2.1. TTF-Annulated Calix[4]pyrroles 2646 2.4. TTF-Annulated Porphyrins 2665
2.1.1. TTF-Annulated Calix[4]pyrroles for Anion 2.4.1. TTF-Porphyrins with Different Numbers
Sensing 2647 of Fused TTF Units 2665
2.1.2. TTF-Annulated Calix[4]pyrroles for Sens- 2.4.2. Quinoxaline-Fused TTF-Porphyrins 2669
ing Neutral Aromatic Electron-Deficient 2.4.3. TTF-Annulated Expanded Porphyrins 2670
Guests 2649 2.5. ExTTF Porphyrins 2671
2.1.3. TTF-Annulated Calix[4]pyrroles for Sens- 2.6. Other Porphyrin−TTF-Based Donor−Accept-
ing Spherical Guests 2653 or Systems 2673
2.1.4. TTF-Annulated Calix[4]pyrroles and Sur- 2.6.1. Donor−Acceptor Systems Based on
face Studies 2656 Porphyrins with Peripheral TTF Substitu-
2.1.5. TTF-Annulated Calix[4]pyrroles for Che- ents Connected through Flexible Organ-
moresponsive Supramolecular Copoly- ic Spacers 2673
merization with Heterocomplementary 2.6.2. Donor−Acceptor Systems Consisting of
Calix[4]pyrroles 2657 Porphyrins with Axially Coordinated TTF
2.1.6. TTF-Annulated Calix[4]pyrroles for Ion- Derivatives 2677
Mediated Reversible Electron-Transfer
(ET) Process in Supramolecular Ensem-
bles Formed with Electron-Deficient
Guests 2661 Special Issue: Expanded, Contracted, and Isomeric Porphyrins
2.2. TTF-Annulated Hybrid Calix[n]pyrrole Sys-
tems 2663 Received: June 15, 2016
Published: October 18, 2016

© 2016 American Chemical Society 2641 DOI: 10.1021/acs.chemrev.6b00375

Chem. Rev. 2017, 117, 2641−2710
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2.6.3. Supramolecular Nonbonded Donor−Ac-
ceptor Ensembles of Porphyrin and TTFs
2.7. TTF-Functionalized Porphyrazines
2.7.1. TTF-Annulated Unsymmetrical and Sym-
metrical Porphyrazines
2.7.2. Porphyrazines Peripherally Modified
with TTFs through Saturated Spacers
2.7.3. Pyrazinoporphyrazine with Peripheral
TTF Units Tethered by Flexible Spacers
2.8. TTF-Functionalized Phthalocyanines
2.8.1. TTF-Annulated Symmetrical Phthalocya-
nines
2.8.2. TTF-Crown-Ether-Functionalized Phtha-
locyanines
2.8.3. TTF-Annulated Unsymmetrical Phthalo-
cyanines
2.8.4. Phthalocyanines Containing Peripheral
TTF Units Connected through Saturated
Spacers
2.8.5. Norphthalocyanines Attached to TTFs
through Saturated Spacers
2.9. TTF-Annulated Subphthalocyanines
3. Conclusions and Future Prospects
Author Information
Corresponding Authors
Notes
Biographies
Acknowledgments
Abbreviations
References
1. INTRODUCTION
Tetrathiafulvalene (TTF) is an effective π-electron-donating
molecule that displays unique electrochemical behavior. These
key attributes have resulted in its extensive use in the
construction of organic conductors. A characteristic feature of
TTF, mirrored in a number of its derivatives, is that, upon
stepwise oxidation, it gives rise to two sequentially oxidized
species, namely, the TTF radical cation (TTF•+) and the TTF
dication (TTF2+). The oxidation is thermodynamically reversible
(cf. Figure 1) within the accessible electrode potential range (viz.,
Figure 1. Reversible redox processes involving the neutral (TTF),
radical cation (TTF•+), and dication (TTF2+) species, respectively.
These redox changes endow TTF with unique photophysical and
electrochemical properties.
on TTF that are attractive in the quest to make electronic
2682 devices,2−11 organic conductors,12 light-harvesting anten-
2684 nas,13−15 optically active materials,16,17 and pigments.18
To frame the seminal insights provided by the iconic R. S.
2684 Mulliken and his charge-transfer theory and R. A. Marcus and his
electron-transfer mechanism in the context of TTF chemistry, a
2687 brief theoretical background is provided here.
In an effort to create efficient donor−acceptor systems (e.g., a
2688 TTF−TCNQ complex), the choice of the electron-donating and
2688 -accepting molecular units in the ensembles is critical.19 Relative
to the acceptor (A), an electron-donor molecule (D) has, in
2688 general, a lower ionization energy (Ip), thereby being oxidized
more readily. In contrast, an electron-accepting molecule (A) has
2691 a larger electron affinity (Ea) and can be reduced at relatively low
potentials. Electronic coupling between the highest occupied
2693 molecular orbital (HOMO) of the donor and the lowest
unoccupied molecular orbital (LUMO) of the acceptor
molecules typically results in a degree of partial charge transfer ρ
2694
diffuse ET diffuse
D + A HoooooI [D···A] HooI [D ρ +···Aρ −] HoooooI D+ + A− (1)
2697
2700 Mulliken conceived that a diffusional encounter between an
2701 electron donor, D, and an electron acceptor, A, would form a
2702 reversible encounter complex (D···A) and worked to correlate
2702 the extent of the interspecies interaction with the observed
2702 optical transition(s).20
2702 In the case where the value of ρ is close to 1, a radical ion pair
2703 (D•+ and A•−) can be obtained through an electron-transfer
2703 (ET) event. ET is a mechanistic description of the thermody-
2704 namic concept of a redox process, wherein the oxidation states of
both reaction partners change. The accompanying electron-
transfer state, [D•+ A•−] is often produced under the conditions
of reversible equilibrium. Therefore, electron back-transfer
generally occurs as well. By far, the most accessible contribution
to the development of ET theory came from Marcus, whose
seminal contributions from 1956 onward were recognized by the
Nobel Prize in Chemistry in 1992.21,22 Marcus’ electron-transfer
formulation provided a major framework for understanding
electron-transfer dynamics.
The charge transfer can be either thermally or optically
induced. It can be described by transitions between, or motions
on, free energy surfaces (FESs).23 The free energy of the whole
electron donor−acceptor system, including the solvent environ-
ment, is given as a function of the reaction coordinate (Figure 2).
Following the Franck−Condon principle, electron motion is
much faster than nuclear motion. As a consequence, optically
induced charge transfer occurs from the minimum of the reactant

E1/21 = +0.34 V and E1/22 = +0.73 V vs Ag/AgCl in acetonitrile).1

TTF is also thermodynamically quite stable in a variety of
different chemical environments (except in the presence of
strong acids and oxidants). Thus, it is widely used as a building
block in the formation of supramolecular structures and organic
charge-transfer (CT) complexes. Functionalization of the TTF
core is often easily achieved and allows for synthetic integration
of the TTF unit into various D−A or D−π−A systems (where D Figure 2. Diabatic (dashed line) and adiabatic (solid line) free energy
stands for donor and A stands for acceptor). This has allowed the surfaces of an electron donor−acceptor system. The optically induced
creation of both inter- and intramolecular CT constructs based (green) and thermally induced (blue) charge transfers are shown.

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state generated by an increase in the energy along the vertical

direction to the product FESs, whereas thermally induced charge
transfer can occur only in the transition-state (TS) region. In the
case of thermally induced charge transfer, the system has to move
along the reaction coordinate to the TS region, resulting in an
activation barrier. The barrier height can be estimated for
optically induced charge transfer using geometric considerations.
The free energy of activation, ΔG‡ET, can be calculated from the
point where the two parabolas intersect
0
‡ (ΔG ET + λtotal)2
ΔG ET =
4λtotal (2)
The free energy difference between the minima of the initial
and final states is represented by ΔG0ET, and λtotal is the total
reorganization energy, which is composed of the inner-sphere
reorganization energies (λv) and outer-sphere (λo) reorganiza-
tion energies. Therefore, λv and λo represent the intramolecular
and solvent coordinate changes, respectively, in the optically
induced charge-transfer process, and the sum ΔG0ET + λtotal is the
total energy needed to induce optically driven charge transfer.
Whereas λv cannot be calculated in a simple manner, λo can
commonly be estimated according to the classic Marcus
expression, where the donors and acceptors are assumed to be
imbedded in a dielectric continuum

e2 ⎛ 1 1 ⎞⎛ 1 1 1⎞
λ0 = ⎜ − ⎟⎜ + − ⎟
4πε0 ⎝ n 2
D ⎠⎝ 2R+ 2R − d⎠ (3)
and the electron-donor and electron-acceptor redox centers R±
are assumed to be spherical. The distance between these redox
centers is represented by d. The solvent continuum is described
by its refractive index n, permittivity D, and dielectric constant ε0.
In the adiabatic case, the free energy of activation, ΔG‡ET, is
reduced in comparison to the diabatic limit. This is a result of the
FES splitting in the TS region.
The rate constant of charge transfer, k, is governed by the
barrier height given by ΔGET ‡
. The probability P can be
rationalized by the time the system needs to cross the TS region
versus the time the system needs to change from the reactant to
the product state. In the diabatic regime, the change of states is
slow as the result of motion required through the TS region.
Thus, the probability for the transition from the reactant to the
product state is low. As a consequence, the overall charge transfer
is limited by P, which, in turn, is proportional to the square of the
electronic coupling element V2. In the diabatic limit, the rate
constant of charge transfer, kna (na = nonadiabatic), can be
described by the Arrhenius-type equation
1 reorganization energies and undergo minimal structural and
k na = 4π 2ℏc 2
4π ℏcλtotalkBT
⎡ ℏc(λ 0 2⎤
total + ΔG )
V 2 exp⎢ − ⎥
⎣ 4λkBT ⎦ (4)
where kB and ℏ are the Boltzmann and Plank constants,
respectively; c is the speed of light in a vacuum; T is the
temperature; and ΔG0 is the free energy difference between the
reactant and product states. In this case, the logarithm of the ET
rate constant (log kna) is related parabolically to the ET driving
force (negative ET free energy change) between the electron
donor and acceptor and the ET reorganization energy, λtotal, that
is, the energy required to structurally reorganize the donor,
acceptor, and their solvation spheres upon ET (Figure 3a).
2643
Figure 3. (a) Schematic diagrams showing different regions described
by the Marcus theory of electron transfer as applied to a D−A system.
(b) Driving force dependence of log kET on different λ values.
Barrierless (i.e., optimal) electron transfer can occur if λtotal =
ΔG0ET. In the normal region associated with Marcus theory, an
increase in the free energy driving force, ΔG0ET, results in a
decrease in the activation energy, ΔG‡ET. A further increase in
ΔG0ET (≈ λtotal) yields the maximum rate of electron transfer.
Eventually, an increase in the driving force leads to an increase in
the activation barrier, ΔG‡ET, and the rate of electron transfer
decreases. This portion of the FES is generally referred to as the
Marcus inverted region (Figure 3b).
A number of electron-donor−acceptor systems containing
porphyrin and phthalocyanine analogues have been prepared in
an effort to control electron-transfer processes. These frame-
works are attractive because of their inherent highly delocalized
electronic structures and the relatively rigid π-scaffolds they
provide. For instance, porphyrins typically display relatively small
solvation changes when used as components in ET couples.24−27
The electronic features of TTF and its derivatives also make
them attractive for ET studies. Synthetic modifications can be
used to modulate their intrinsic donor−acceptor characteristics,
making TTF-based systems attractive as strong electron donors
in both static and dynamic supramolecular motifs. Pyrrolo-TTF
systems have had a particularly important role to play in the latter
context.
In recent years, considerable effort has been devoted to the
construction of various supramolecular architectures displaying
controlled molecular movement triggered by external stimuli
such as specific acids, anions, and a variety of guest molecules.
For the most part, the designs have been based on the use of
receptors with strong affinity toward guest molecules and have
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Chart 1. Representative TTF-Annulated Oligopyrrolic Macrocycles
relied on a variety of noncovalent interactions (e.g., hydrogen-
bonding, electrostatics, and π−π D−A-based effects). TTF has
proved to be a near-ideal molecular component in such systems.
It has been exploited in the design of many different
supramolecular architectures, including molecular ma-
chines,28−32 molecular flasks,33,34 molecular tweezers,35−37 and
molecular switches.38−46
Some of the resulting constructs have potential applications as
sensors for organic neutral guests and hazardous nitroaromatic
compounds (vide infra). Generally, the observed sensing
behavior arises from the formation of supramolecular ensembles
by specifically designed guests with TTF-annulated hosts, which
can be detected spectroscopically or electrochemically at the
micro- to nanomolar levels. These hybrid systems are particularly
important because they contain both a redox-active site and a
chromophoric unit that jointly or separately provide for an
efficient spectroelectrochemical or photophysical response to the
targeted analyte. In many instances, TTF functionalization of a
receptor serves to enhance the overall electron-donor strength of
the resulting supramolecular construct compared to non-TTF-
based systems. This modification often provides for enhanced
hydrogen-bonding or π−π interactions with anions and electron-
deficient guests. Moreover, as detailed further below, fusion of a
TTF subunit to a calix[4]pyrrole core can give rise to molecular
containers with concave openings suitable for encapsulating
spherical guest molecules. In addition, TTF annulation to a
2644
Review
highly conjugated macrocyclic core (e.g., porphyrin, porphyr-
azine, and phthalocyanine) allows TTF chemistry to be
combined with porphyrin chemistry to produce hybrid systems
with many interesting photophysical and electrochemical
properties. Therefore, these systems are a primary point of
focus in this review.
TTF-derived compounds have been widely described in book
chapters,12,47 accounts,48 feature articles,27,49,50 and review
articles.1,51−72 A few of the recent review articles60,73 discuss
TTF oligomers and fused TTF derivatives. Some of the
reviews74−79 emphasize the synthesis and properties of various
TTF derivatives with different functionalities. There are also a
couple of review articles on TTF-based cyclophanes and cage-
motif systems,80 as well as those detailing D−A assemblies and
their potential use in the areas of molecular materials and
devices.81−85 Other reviews focus on the charge-transfer and
energy-transfer properties of TTF systems and their potential in
the areas of organic electronic materials86−89 and magnetic
materials.90 However, to the best of our knowledge, a detailed
review focused on TTF-annulated oligopyrrolic macrocyclic
systems has yet to appear in the literature. Given the utility of
these systems in the areas of ET study, molecular recognition,
supramolecular materials chemistry, and sensor development, we
believe that a comprehensive review is warranted. Therefore, our
vision is to highlight the most recent developments involving
various TTF-annulated oligopyrrolic macrocyclic compounds,
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Scheme 1. Synthetic Routes Leading to Various TTF-Annulated Pyrroles
including TTF-calix[n]pyrroles (where n = 4, 5, and 6), TTF-
porphyrins, so-called exTTF-porphyrins, TTF-porphyrazines,
TTF-phthalocyanines, and TTF-subphthalocyanines, as well as
several closely related structures (Chart 1).
In particular, we have made efforts to discuss in detail the
supramolecular recognition and charge-transfer properties of
nonaromatic TTF-pyrrole systems, with an emphasis being
placed on the detection and sensing behavior of these
2645
Review
macrocycles as reported over the past two decades. We also
summarize work focused on TTF-fused porphyrins, as well as
several extended TTF analogues that contain formal porphyrin
bridges (termed exTTF porphyrins).
All of these oligopyrrolic macrocyclic compounds containing
TTF(s) are potential electron donors capable of complexing a
wide range of electron-poor guests. Their sensing behavior
mainly reflects their ability to form supramolecular D−A-type
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Chart 2. Chemical Structures of Various TTF-Annulated Calix[4]pyrrole Receptors and the Reference Compound C[4]P
assemblies. As a general rule, the efficiency whereby such D−A
supramolecular ensembles are formed depends strongly on the
electronic nature of the components, the three-dimensional
arrangement of the planar TTF units within the macrocyclic
receptor and guest, and the environment surrounding the self-
assembled complex.
In the first part of this review, we discuss the design and
synthesis of TTF-annulated pyrrolic precursors before turning to
calix[4]pyrroles containing TTF subunits, as well as their higher
analogues. TTF-calix[n]pyrroles are structurally flexible systems
wherein a number of TTF units are fused to the periphery of the
core macrocycle. As detailed further below, they are often capable
of sensing anions, detecting nitroaromatic explosives, and
recognizing a variety of guest molecules. The electrochemical
response and photophysical behavior of these systems are also
discussed thoroughly. In some cases, the reversible switching of
an electron-transfer process within a supramolecular ensemble as
a function of guest molecules is considered. The effects of
metalation and various guest inputs and their effects on the
structure and properties of a few highly flexible hybrid
calixpyrrole systems are also highlighted. In the second part,
we focus on TTF-fused porphyrins, as well as higher-order TTF-
derived porphyrins and their artificial photosynthetic applica-
tions. We also discuss the use of specific guest inputs to control
charge-transfer (CT) phenomena in the case of TTF-fused
porphyrins. The interesting ground-state and excited-state
dynamics, as well as electrochemical behavior, that originate
from the presence of a chromophoric porphyrin subunit and one
or more redox-active TTF groups are also detailed. The
electrochemical and optical properties of various TTF-fused
porphyrazines, phthalocyanines, and subphthalocyanines are
discussed thoroughly in the last part of this review. Every effort
has been made to cover the literature through early 2016.
2. TTF-ANNULATED OLIGOPYRROLIC MACROCYCLIC
COMPOUNDS
2.1. TTF-Annulated Calix[4]pyrroles
Annulation of a TTF unit onto a pyrrole scaffold through the
β,β′-positions has a significant effect of the acidity of the pyrrolic
NH proton because of the inductive effect of the sp2-hybridized S
atoms and the intrinsic electron-rich nature of the TTF subunit.
2646
Review
The resulting TTF-annulated pyrrole derivative represents a
useful new building block that can bring both rigidity and
electron-donating character to various types of oligopyrrolic
macrocycles (e.g., porphyrins, calixpyrroles). When it is
incorporated into a calix[n]pyrrole (n = 4, 5, and 6) framework,
higher binding affinities toward anions as the result of NH−
anion hydrogen-bonding interactions are generally observed.
The peripheral TTF unit can also be utilized as secondary
interaction sites by providing a set of electron-rich π-surfaces.
From the viewpoint of the pyrrolic TTF building block and
systems created from it, modification of the terminal side of the
TTF unit (i.e., that farthest from the pyrrole NH proton) can
allow for further fine-tuning of the electronic structure. Common
functionalized TTF pyrrole derivatives are provided by benzo
annulation and thioalkyl substitution. These two substitution
patterns have received particular attention because they provide a
reasonable balance between solubility in organic solvents and
chemical stability of the derivatives. However, other substituted
analogues are known.
A key step in making a TTF-annulated oligopyrrolic
macrocyclic system is the synthesis of a TTF-fused pyrrole
precursor specifically designed for the particular macrocyclic
target in mind. Approaches used to prepare a few well-studied
TTF-annulated pyrroles (e.g., PnS-TTF-pyrrole,91 MeS-TTF-
pyrrole,91,92 PrS-TTF-pyrrole,93,94 BTTF-pyrrole,95 TTTF-
pyrrole,95 TTF-dipyrrole91,92,94) are outlined in Scheme 1.
Typically, the synthesis of TTF-pyrroles involves a CC
bond-forming reaction carried out in triethylphosphite, P(OEt)3,
involving the coupling between an appropriately chosen 1,3-
dithiole-2-thione and N-tosyl-(1,3)-dithiolo[4,5-c]pyrrol-2-one
(OX) derivatives. This is an approach that has proved useful in
obtaining unsymmetrical cross-coupling products (e.g., PrS-
TTF-pyrrole, BTTF-pyrrole, and TTTF-pyrrole). The requisite
heterocoupling often proceeds well because the corresponding
symmetrical products require a homocoupling of either the 1,3-
dithiole-2-thione or OX components. Although these latter
homocouplings can be exploited to obtain species, such as TTF-
bridged bis-pyrroles (TTF-dipyrrole), to date, the products in
question have not been exploited extensively in the preparation
of more elaborated products. This stands in contrast to what is
true for the pyrrolic heterocoupling products. Generally, the
pyrrole nitrogen is tosylated. Detosylation using sodium
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Scheme 2. Synthesis of Various TTF-Calix[4]pyrroles
methoxide (NaOMe) proceeds well, with the result that several
key TTF-pyrrole precursors are now routinely synthesized in the
authors’ laboratories on gram scales.
2.1.1. TTF-Annulated Calix[4]pyrroles for Anion Sens-
ing. In 2003, Becher and co-workers reported the first
calix[4]pyrrole system fused with TTF, the mono-PnS-TTF-
calix[4]pyrrole receptor 1 (Chart 2), which was produced as a
possible electrochemical sensor for anions.96 Compound 1 was
produced through a straightforward synthetic procedure that
involved the BF3·OEt2-catalyzed macrocyclization of a bis-
hydroxymethyltripyrrane with pentylthio-TTF-pyrrole (PnS-
TTF-pyrrole) in a 1:1 stoichiometric ratio, as outlined in
Scheme 2A.
Representative target-oriented synthetic routes used to
prepare other TTF-annulated calix[4]pyrrole receptors are
shown in Scheme 2B. For instance, the symmetrical TTF-fused
calix[4]pyrrole 4 was synthesized by the acid-catalyzed cyclo-
2647
Review
tetramerization of PrS-TTF-pyrrole in acetone; after purification,
this product was isolated in 18% yield.
The anion-recognition properties of receptor 1 were
investigated by means of NMR spectroscopic titrations and
electrochemical analyses. The Job’s plots obtained upon the
titration of 1 with a number of anion salts exhibited maxima at a
mole fraction of 0.5, as would be expected for the formation of
1:1 complexes. An electrochemical response toward different
anions was seen for 1 and was considered to be enhanced by the
presence of a relatively more acidic −NH proton present in the
PnS-TTF-pyrrole subunit because of the presence of a TTF
fragment that is electron-rich relative to a normal pyrrole
(C[4]P; Chart 2). The binding constants corresponding to the
interaction of 1 with halide anions F−, Cl−, and Br− (as the tetra-
n-butylammonium, TBA+, salts) were determined from 1H NMR
spectroscopic titration data obtained at 300 K; the results are
summarized in Table 1. The underlying experiments involved
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Table 1. Binding Constant Values Corresponding to the result of the strong hydrogen-bonding interactions between the
Interaction of Receptor 1 with Various Anions pyrrolic protons and the bound anionic guest (Figure 5).
anion Kab (M−1)
−
F 2.1 × 106
Cl− 1.2 × 105
Br− 7.6 × 103
a
Underlying NMR spectroscopic titrations were carried out using
tetra-n-butylammonium (TBA+) salts of the corresponding halides at
300 K. Binding constant values were obtained by the nonlinear curve-
fitting computer program EQNMR and is the average of two
independent experiments using the chemical shifts of the three
−NH protons as the probe signals. The estimated error was <10%.
b
CD3CN/0.5% v/v D2O.

monitoring the change in the chemical shifts of the resonances

associated with the three nonequivalent −NH protons of the
macrocyclic core as the amount of the corresponding
tetrabutylammonium halide salt was increased. The data were
then fitted to a 1:1 binding profile.
It was also demonstrated that the redox-active TTF unit of this
receptor 1 respond in diagnostic fashion upon complexation with
anions such as Br− in MeCN. This is evident (Figure 4) in terms

Figure 5. Two conformational structures of tetrakis-TTF-calix[4]-

pyrrole, 4. The conversion between these limiting forms is thought to
underlie much of their interesting chemical behavior. (This figure is
based on one that originally appeared in ref 98 but has been redrawn.)

The distinct dynamic motion of TTF-calix[4]pyrrole demon-

Figure 4. (a) Cyclic voltammograms of receptor 1 (0.5 mM) recorded
strated in Figure 5 shows that, in the absence of anions, the
upon the incremental addition of tetra-n-butylammonium bromide system adopts a 1,3-alternate conformation, whereas in the
(TBABr) in MeCN at 298 K using tetra-n-butylammonium presence of anions (e.g., Cl−), a cone-shaped conformer is
hexafluorophosphate (TBAPF6, 0.4 M) as the supporting electrolyte thermodynamically preferred as a result of strong hydrogen-
at a scan rate of 0.5 V s−1. (b) CV titration results showing the cathodic bonding interactions with the bound Cl− guest.
shift of the first oxidation potential of receptor 1 seen upon the gradual In the case of compounds 2 and 4, X-ray crystallographic
addition of Br− ions. Note that the cathodic shift of the first oxidation analyses (Figure 6) served to reveal that, in the absence of any
potential is independent of the second oxidation process. (Reproduced added anion, the systems adopt a 1,3-alternate conformation
with permission from ref 96. Copyright 2003 Wiley-VCH Verlag similar to those of other normal nonannulated calix[4]pyrrole
GmbH.) systems, such as C[4]P.
Anion-binding studies carried out in organic media [1,2-
dichloroethane (DCE)] using soluble anion salts served to
of a cathodic displacement of the first oxidation potential (E1/21), demonstrate that incorporation of one or more electron-rich
along with an increase in the current intensity associated with the
second TTF-based oxidation potential (E1/22), as determined by
cyclic voltammetry (CV). This makes receptor 1 a very efficient
redox-responsive chemosensor for halide anions in this organic
medium.
Jeppesen and co-workers reported a series of TTF-substituted
calix[4]pyrrole receptors, 2−4, which were also tested as
potential electrochemical sensors.97 Among these, receptor 4
exhibited many interesting chemical and photophysical features
that were ascribed in large measure to its ability to adopt two
different limiting conformations, namely, the (i) 1,3-alternate
and (ii) cone conformers in the absence and presence of anions,
respectively. In the absence of anions, the 1,3-alternate form is Figure 6. Solid-state structures of (a) mono-TTF-calix[4]pyrrole (2)
energetically favorable, as it is for most other calix[4]pyrroles, and (b) tetrakis-TTF-calix[4]pyrrole (4), showing the 1,3-alternate
whereas in the presence of coordinating anions, such as Cl−, conformers. (This figure was redrawn using data that were originally
these systems adopt the corresponding cone conformation as a published in ref 97.)

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TTF subunits into the calix[4]pyrrole backbone improves the
anion-binding abilities of the receptors while also affecting their
selectivity (Table 2).
Table 2. Binding Constants (Ka, M−1) Corresponding to the
Interactions between Receptors 2, 3, and 4 and Different
Anions as Determined by Isothermal Titration Calorimetry
(ITC) at 298 K in DCE
anion 2 3 4
Cl− 1.2 × 105 6.6 × 105 2.5 × 106
Br− 2.2 × 103 8.3 × 103 5.8 × 104
CN− 8.5 × 104 2.6 × 105 1.1 × 106
NO2− 6.9 × 104 2.8 × 105 1.2 × 106
MeCO2− 6.5 × 104 3.9 × 105 1.3 × 106
a
Estimated errors are <10%. bReceptors 2, 3, and 4 were titrated with
the tetra-n-butylammonium salts of the anion in question so as to
obtain the heat effects corresponding to complexation. The net heat
effect was determined by subtracting the heat traces for the
appropriate background titration.
For instance, the binding constant for Cl− (as the TBA+ salt) in
the case of 4 is significantly enhanced (i.e., Ka = 2.5 × 106 M−1)
compared to that of either C[4]P or 2 (i.e., 3.5 × 104 M−1 for
C[4]P and 1.2 × 105 M−1 for 2). As the number of TTF-pyrrole
units increases, the binding constants for anions likewise
increase. These findings are consistent with the notion that the
presence of electron-donating TTF units within this class of
receptors serves to strengthen the NH−anion hydrogen-bonding
interactions. The effect can be further enhanced by the presence
of electronegative sp2-hybridized sulfur atoms in this particular
set of receptors. This putative electronic effect was also seen in
the case of other anions (e.g., Br−, CN−, NO2−, and MeCO2−).
Of note is that halide complexation could also be monitored by
electrochemical means. For instance, clear potential shifts in the
TTF-based redox waves were observed as a function of anion
concentration (Figure 7).
It was observed that, upon addition of 0.2 equiv of n-Bu4NCl
(as the source of Cl−) to receptor 2 in 1,2-dichloroethane at 298
K (Figure 7a), a new peak at E1/21 = −0.11 V appeared in the
region associated with the first oxidative event. This new peak is
ascribed to oxidation of the complex formed as the result of
chloride-anion binding, namely, 2·Cl−. Further addition of Cl−
ions led to a monotonic decrease in the intensity of the original
peak at E1/21 = +0.032 V assigned to oxidation of the
uncomplexed form (i.e., free receptor 2) with a concurrent
increase in the intensity of the new peak appearing at E1/21 =
−0.11 V. A total displacement (ΔE) of −145 mV of the first
oxidation potential was observed in this case. The buildup in the
signal at E1/21 = −0.11 V was considered to reflect an increase in
the relative concentration of the complex (2·Cl−) at the expense
of that of the uncomplexed receptor 2. In the case of receptor 3,
gradual addition of n-Bu4NBr (as the source of Br− anion) under
identical experimental conditions resulted in a slight negative
shift (Figure 7b) of the first oxidation potential (E1/21) associated
with the TTF units. It was also noticed that, upon increasing the
Br− concentration, the intensity of current associated with the
second oxidation wave gradually increased. This was rationaized
in terms of the Br− ions being oxidized to Br2 under these
conditions. The displacement of the first oxidation potential
reached a limit of ΔE = −70 mV at the point where
approximately 1 stoichiometric equiv of Br− ion had been
added to the solution containing receptor 3. In the case of
2649
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Figure 7. Cyclic voltammograms of 0.25 mM 1,2-dichloroethane
(DCE) solutions of receptors (a) 2, (b) 3, and (c) 4 recorded vs Fc+/Fc0
in the presence of increasing quantities of TBAX (in the case of
receptors 2 and 4, X = Cl−; for receptor 3, X = Br−). Experiments were
carried out at 298 K using TBAPF6 (0.1 M) as the supporting electrolyte.
(Reproduced with permission from ref 97. Copyright 2006 American
Chemical Society.)
receptor 4, a shift in the first oxidation potential to a limit of ΔE =
−30 mV was seen (Figure 7c) upon the incremental addition of
n-Bu4NCl. The largest shift in the first oxidation potential, ΔE =
−145 mV, was observed in the case of receptor 2 when titrated
with Cl−. Although the degree of response clearly varies in
qualitative terms, all of these TTF-functionalized macrocyclic
receptors behave as rudimentary electrochemical sensors for the
Cl− and Br− anions.
2.1.2. TTF-Annulated Calix[4]pyrroles for Sensing
Neutral Aromatic Electron-Deficient Guests. The rationally
designed TTF-annulated calix[4]pyrrole system 4 also acts as an
effective receptor for 1,3,5-trinitrobenzene (TNB), tetrafluoro-p-
benzoquinone, tetrachloro-p-benzoquinone, and p-benzoqui-
none in CH2Cl2 solution.98 This neutral substrate recognition
process can be blocked by the addition of chloride anion.
Receptor system 4 was designed to take advantage of the fact that
calix[4]pyrroles generally exist in the 1,3-alternate conformation
in the absence of anions. In this latter conformation, each pair of
identical TTF electron donors is expected to hold an electron-
deficient guest in a sandwich-like fashion through D−A−D-
based CT interactions (Figure 8a). Additional stabilization is also
provided by pyrrole NH−substrate hydrogen-bonding inter-
actions. Based on a range of experimental findings, including X-
ray structural analyses, limiting binding modes were deduced for
receptor 4 interacting with various electron-deficient species,
including the model electron-deficient nitroaromatic explosive
1,3,5-trinitrobenzene (TNB) and tetrafluoro-p-benzoquinone.
These interactions are shown for TNB in Scheme 3, along with
the changes seen upon changes in treatment conditions. An X-ray
structure of the complex between 4 and 2 equiv of TNB is shown
in Figure 8a.
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Figure 8. (a) X-ray structure of the supramolecular complex (TNB)2⊂4.
(b) UV−vis−NIR spectral changes seen for mixtures of 4 and TNB
under various experimental conditions. (Reproduced with permission
from ref 98. Copyright 2004 American Chemical Society.)
An intermolecular CT band at λmax = 677 nm was seen in the
UV−vis−NIR absorption spectrum (Figure 8b) when 4 was
treated with TNB. This band disappeared upon addition of Cl−.
This was taken as evidence that an anion-induced conformational
change leads to a guest-release process and a breakup of the initial
CT complex. After removal of the anion by means of an aqueous
wash, the initial sandwich structure was restored, along with the
low-energy CT-visible absorption feature.
Scheme 3. Proposed Supramolecular Host−Guest Chemistry Involving Receptor 4 and TNB Guest Observed under Different
Experimental Conditions
2650
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Positive Homotropic Allosteric Binding Properties of TTF-
Calix[4]pyrrole Derivatives with Electron-Deficient Nitro-
aromatic Guests. The design and construction of artificial
receptors displaying nonlinear amplification as a result of an
initial guest binding event represents a well-appreciated
challenge in supramolecular chemistry. As above, compound 4
was found to bind polynitroaromatic explosives with a 1:2
(receptor/guest) stoichiometry in organic solvents in the
absence of a coordinating anion, such as Cl−. However, it was
also found that the binding affinity of 4 for electron-deficient
guests is somewhat modest. As a consequence, relatively high
guest concentrations are needed to produce a naked-eye-
detectable colorimetric response. To overcome this deficiency,
aromatic (thiophene and benzene) annulated tetrakis-TTF-
calix[4]pyrroles, namely, 5 and 6, were synthesized, and their
abilities to bind polynitroaromatic explosives, including TNB,
picric acid (TNP), and 2,4,6-trinitrotoluene (TNT), were tested.
A careful analysis of the colorimetric changes observed when
TNB, TNP, and TNT were allowed to react with 4−6 revealed a
positive homotropic allosteric effect (K1 < K2).95 Figure 9
illustrates the proposed origin of this positive homotropic
allosteric effect in the case of receptor 5 and TNP. Briefly, the
effect is explained by the fact that binding of a first guest forces
the inherently flexible host systems to adopt a more rigid 1,3-
alternate structure. This, in turn, leads to a loss of rotational
freedom, resulting in a preorganized receptor structure that is
better able to encapsulate the second target guest molecule.
Based on quantitative analyses of visible spectroscopic titration
results, receptor 6 was found to display a greater degree of
positive homotropic allostery than the other systems, for which a
general trend of 6 > 5 > 4 was found (Table 3).
Zhu et al. reported a TTF-calix[4]pyrrole 6 that displayed a
colorimetric response toward polynitroaromatic explosive both
in chloroform solution and when incorporated on a polymer
microcantilever with an integrated deflection-sensing element.99
This work represents an approach to creating a practical device
capable of stand-off detection of nitroaromatic explosive vapors.
It was also expected that the microcantilever systems would
display enhanced sensitivity and improved detection limits
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Chemical Reviews Review

Figure 9. Proposed origin of the positive homotropic allosteric effect observed in the case of 5 and TNP. (This figure was redrawn using data that were
originally published in ref 95.)

Table 3. Microscopic Association Constants, and achieved. This represents an improvement in the detection limit
Cooperativity Parameters for the Receptors 4, 5, and 6 with of at least 30-fold compared to the colorimetric detection limit of
Various Nitroaromatics (TNB, TNP, and TNT) 0.3 ppm for TNB measured in chloroform solution using
compound Ka (M−2) n K1 (M−1) K2 (M−1) K2/K1 receptor 6. This study provides an indication that stand-alone
4·2TNB 4.3 × 103
1.27 3.9 × 102
1.4 × 103
3.6 colorimetric receptors could potentially be translated into
4·2TNP 3.8 × 103 1.30 2.8 × 102 1.2 × 103 4.1 practical devices with improved sensitivities by incorporating
4·2TNT 3.3 × 102 1.23 5.9 × 101 2.0 × 102 3.3 them into cantilever sensor arrays.
5·2TNB 1.5 × 105 1.34 2.8 × 103 1.7 × 104 6.2 Self-Assembly Driven Sensing of TNB with a TTF-Calix[4]-
5·2TNP 9.1 × 104 1.34 1.7 × 103 1.1 × 104 6.5 pyrrole Receptor. Nielsen and Stein reported the synthesis and
5·2TNT 1.2 × 104 1.31 5.7 × 102 2.6 × 103 4.5 binding properties of a TTF-calix[4]pyrrole receptor 7 appended
6·2TNB 3.4 × 106 1.70 1.3 × 103 3.1 × 104 24 with an electron-deficient 3,5-dinitrobenzoate guest moiety.100
6·2TNP 3.7 × 106 1.86 6.4 × 102 2.0 × 104 31 Preliminary spectroscopic studies revealed that the receptor self-
6·2TNT 2.3 × 104 1.45 3.2 × 102 2.8 × 103 10
a
associates into a dimer (7·7) at high concentration (Scheme 4).
Based on absorption spectroscopic titrations of the respective hosts The self-association of the receptor leads to preorganization in its
(0.20 mM) in CHCl3 at 298 K. bEstimated error for calculated binding
constants is ≤12%. 1,3-alternate conformation. As a result, dimer 7·7 displays an
approximately 2-fold higher binding affinity for nitroaromatic
relative to what was previously been found in the solution state. analytes (e.g., TNB) than the model receptor 4. This binding, in
In fact, a detection limit for TNB vapor of less than 10 ppb was turn, leads to the formation of a supramolecular ensemble

Scheme 4. Proposed Mechanism for the Self-Assembly of a TTF-Calix[4]pyrrole Derivative Driven by Complexation

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TNB2⊂7·7 that is stabilized through CT and hydrogen-bonding
interactions.
UV−vis−NIR spectral titrations with various anions (as their
TBA + cation salts) were carried out at two different
concentrations of receptor 7.101 It was found that, at higher
concentrations [(0.15−0.40) × 10−3 M], the proposed anion-
binding events could be monitored spectroscopically in terms of
the progressive disappearance of the CT band centered at 560
nm that occurs upon the incremental addition of coordinating
anions, such as chloride. At lower concentrations of 7 [(6−7) ×
10−6 M], the absorption band centered at 326 nm was used to
determine the binding constants. The resulting values are given
in Table 4. An inspection of the data in this table reveals that the
Table 4. Binding Constants (Ka, M−1) Corresponding to the
Interactions between the Receptor System 7 and the Parent
System 4 with Different Anions as Determined by Absorption
Spectroscopy and Isothermal Titration Calorimetry (ITC) in
CH2Cl2 at 298 K
anion 7 (326 nm)d 7 (600 nm)d 4 (ITC)
−
Cl 2.55 × 106
8.5 × 105
2.5 × 106
Br− 5.55 × 104 3.5 × 104 5.8 × 104
CN− 4.65 × 105 2.4 × 105 1.1 × 106
MeCO2− 5.35 × 106 nde 1.3 × 106
a
Estimated errors are <15%. bReceptors 7 and 4 were titrated with the
tetrabutylammonium salts of the anion so as to obtain the heat effects
corresponding to complexation. cNet heat effect was determined by
subtracting the heat traces for the appropriate background titration.
d
Experiments were monitored at different wavelengths. eNot
determined.
association constants obtained from the absorption spectro-
scopic studies carried out at low receptor concentrations match
well those obtained from isothermal titration calorimetry (ITC)
studies of the parent system 4. In contrast, the binding constants
obtained at high concentrations of 7 are lower. This is taken as
evidence that, at high concentrations, self-association serves to
produce dimer 7·7, thus diminishing the inherent propensity to
recognize anions.
Acid−Base-Induced Switching of a TTF-Calix[4]pyrrole
Receptor and Evidence for a Positive Cooperative Effect.
Nielsen et al. also reported an acid−base-controllable “molecular
Scheme 5. Acid−Base-Controlled Supramolecular Guest Binding Using an Unsymmetrical Receptor
2652
Review
switch” consisting of the asymmetric TTF-calix[4]pyrrole
derivative 8 that displayed responsive binding behavior in the
case of TNB recognition.102 This receptor consists of three
identical TTF-pyrrole units and a fourth TTF-pyrrole unit
appended with a phenol moiety. It is worth noting that the
asymmetric system 8 was prepared by simply condensing two
different TTF-annulated pyrroles in accord with the normal one-
pot synthetic strategy used to produce analogue 4. The host−
guest interactions between 8 and TNB were studied by means of
absorption and 1H NMR spectroscopies. The underlying studies
revealed that the molecular receptor could be switched between
limiting locked and unlocked states by using base and acid as the
inputs (Scheme 5).
In the unlocked state, the receptor is able to accommodate two
TNB guest molecules through strong hydrogen-bonding
interactions with the NH protons, as well as interactions
between the electron-donating TTF units and the electron-
deficient TNB guest molecules. In contrast, TNB guests are not
able to bind appreciably to the receptor in the locked state in
which the phenolate anion strongly coordinate with the NH
protons to construct a partial cone-like conformer. The addition
of acid serves to protonate the phenolate anion and restores TNB
binding.
Coordination-Driven Switching of a Preorganized and
Cooperative TTF-Calix[4]pyrrole Receptor. Nielsen and co-
workers also reported a metal-ion-coordination-triggered switch-
ing system103 that consists of a preorganized asymmetric TTF-
calix[4]pyrrole receptor, 9, bearing an appended pyridine moiety
(Scheme 6). This system utilizes intramolecular hydrogen
bonding between the pyrrole NH protons and the pyridine
nitrogen atom to switch off TNB binding in the 1,3-alternate
conformation and metal-based complexation of the pyridine
moiety to turn it back on.
Absorption and 1H NMR spectroscopic data analyses along
with theoretical calculations revealed that the system has the
ability to complex electron-deficient nitroaromatics, such as
TNB, and that the binding events could be reversibly modulated
by using Zn2+ as an external stimulus. In the free state (i.e., in the
absence of Zn2+), the receptor system is locked into a relatively
higher level of preorganization as a result of the intramolecular
hydrogen-bonding interactions (self-complexation) between the
pyrrole NH protons of the TTF-calix[4]pyrrole skeleton and the
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Scheme 6. Proposed Mechanism for the Coordination-Driven Host−Guest Complexation Seen in the Case of Receptor 9

pyridine moiety attached to one of the TTF side arms. In this Scheme 7. Illustration of Proposed Binding Mode of DNT
particular conformation, the receptor displays negative cooper- Guests Seen in a Cantilever System Based on Receptor 4
ativity in that initial TNB binding is more facile than subsequent
binding events. Specifically, the binding of a second molar
equivalent of TNB requires displacement of the appended
pyridine, which is held in place by hydrogen-bonding
interactions as noted above. Addition of hexafluoroacetylaceto-
nato Zn(II), [Zn(hfac)2], to the system provides a Lewis acid
(Zn2+) that interacts with the appended pyridine moiety. This
allows the parent receptor to revert to the more conformationally
flexible state characteristic of calix[4]pyrroles. Therefore,
addition of Zn2+ induces positive cooperativity in the binding
of TNB by receptor 9.
Bosco et al. reported a modified DVD platform for high-
throughout detection of 2,4-dinitrotoluene (DNT) wherein
silicon cantilevers were functionalized with the receptor system
4.104 Scheme 7 shows the proposed guest binding mode for this
cantilever system.
It was observed that a significant cantilever deflection occurred
when the functionalized cantilever was exposed to DNT.
Moreover, a change in the resonance frequency was detected,
presumably reflecting the added mass resulting from the
encapsulation of DNT within the cantilever system. The DNT
detection capability of this functionalized cantilever system,
which was standardized using reference cantilever systems, was
verified both in aqueous media and in the gaseous phase. Very
good reproducibility was seen, with over 80% of the independent
cantilevers displaying the same bending behavior when
monitored under the same conditions but using different
experimental batches (Figure 10).
2.1.3. TTF-Annulated Calix[4]pyrroles for Sensing
Spherical Guests. Jeppesen and co-workers developed a self- Originally, it was proposed that the fullerene binding was in
assembled multicomponent molecular host system based on 4105 the form of a 2:1 receptor/substrate complex (Scheme 8). This
that was found to interact with the electron-deficient acceptor inference was based on continuous-variation studies (Job plots)
C60 in the presence of a chloride anion source. wherein the total concentration of 4·Cl− and C60 was kept
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Figure 10. (a) Gas-phase detection of DNT. Each curve reports the
average differential signal between a set of 4-treated cantilevers (16
cantilevers) and a set of reference cantilevers (8 cantilevers). Toluene
was used as a control analyte. (b) Solution-phase detection of DNT
guests studied using a continuous flow method in aqueous media. The
plots were generated by averaging the signals obtained using one
functionalized chip (8 cantilevers) and one blank reference chip (8
cantilevers). The vertical gray line indicates the point where the system
is exposed to an aqueous DNT solution. (Reproduced with permission
from ref 104. Copyright 2012 Elsevier Ltd.)
constant. However, it was subsequently appreciated106 that,
because the concentrations of both 4 and Cl− were varied during
the underlying titrations, a systematic error was introduced that
led to the assignment of an incorrect binding stoichiometry. This
followup study provides a discussion of some of the caveats
associated with using Job plots to infer stoichiometries when
more than two guests can be bound to a single receptor. A
solution specific to the analysis of receptor 4 was to use anion
concentrations sufficient to maintain the cone conformation
when studying the interactions with C60. On the basis of these
controlled continuous-variation studies and solid-state analyses
(vide infra), the binding mode, simple 1:1 complexation of the
C60 within the calix[4]pyrrole cup, is now considered to be
established (Scheme 9). Apart from the complex stoichiometry,
other aspects of the initial study, particularly the visible,
spectroscopic, and electrochemical findings, are considered
correct. These latter findings are discussed below.
The importance of anion binding to the calix[4]pyrrole
framework, a predicate for forming a supramolecular complex
with the fullerene guest, was recognized at the time of the initial
report. For instance, no significant absorption is seen for receptor
system 4 or C60 guest molecule in dichloromethane solution
beyond λmax ≥ 550 nm. However, when C60 is added to receptor
4 in the presence of a Cl− anion source (which transforms the
1,3-alternate structure to the corresponding bowl-shaped
conformer), the solution turns green immediately on the
laboratory time scale as a result of the formation of more
ordered multicomponent supramolecular ensemble. The
absorption spectrum of this complex, which was subsequently
assigned to C60⊂4·Cl−, is characterized by a strong CT band with
λmax = 725 nm. In contrast, the addition of 2 equiv of receptor 4 in
its anion-free 1,3-alternate conformation to a solution of C60 in
2654
Review
dichloromethane produces a brown solution. This solution is
characterized by the presence of a weak, broad absorption band
centered at about λmax = 748 nm (ε = 500 M−1 cm−1) in the
visible spectral region (Figure 11b, curve iv), as would be
expected if only minimal intermolecular interactions between
C60 and 4 existed. However, the addition of 5 equiv of TBACl to
this 2:1 mixture of 4 and C60 resulted in an instantaneous color
change from brown to green and the appearance of a strong CT
absorption band (Figure 11b, curve iii, centered at λmax = 725 nm;
ε = 1900 M−1 cm−1). Such a finding provides support for the
proposal that C60 is encapsulated only after 4 undergoes a change
from the 1,3-alternate conformation to the corresponding
chloride-bound cone conformation (i.e., 4·Cl−).
Electrochemical investigations revealed that, upon complex
formation, the first reduction of C60 shifts by −74 mV relative to
that of native C60. This finding supports the proposed donor−
acceptor interactions and the partial shifting of electron density
from the electron-rich TTF subunits to the electron-deficient C60
guest (Table 5). Furthermore, time-resolved femtosecond
transient absorption spectroscopy revealed that, upon photo-
excitation, the electron-transfer rate between 4 and C60 is high
(i.e., the half-life for ET on the order of 1012 s−1).
The formation of the proposed supramolecular complex can
be easily inferred from the prominent visual color changes
relative to its constituents. No significant absorption was noticed
for the receptor system 4 and the C60 guest molecule beyond λmax
≥ 550 nm. However, when 0.5 equiv of C60 was added to receptor
4 in the presence of a Cl− anion source (which served to
transform the 1,3-alternate structure to the corresponding bowl-
shaped conformer), the color of the solution turned green
immediately on the laboratory time scale as a result of the
formation of a more ordered multicomponent supramolecular
ensemble that is now known to have a net stoichiometry of
C60⊂(4·Cl−) [and not C60⊂(4·Cl−)2 as originally assigned]. The
absorption spectrum of this complex gives a strong CT band with
λmax = 725 nm (Figure 11b). Addition of 2 equiv of the yellow
receptor 4 in its 1,3-alternate conformation (that is, in the
absence of chloride anions) to a magenta solution of 0.5 equiv of
C60 in dichloromethane produced a brown solution (Scheme 9).
Jeppesen and co-workers reported a couple of environmentally
responsive, supramolecular switching devices107,108 (Schemes 10
and 11) consisting of receptor 4 and a number of neutral guest
molecules, such as planar or quasiplanar nitroaromatic guests,
including TNB (A), methyl-2,5,7-trinitrofluorenone-4-carbox-
ylate (B), and methyl-2,5,7-trinitrodicyanomethylenefluorene-4-
carboxylate (C), as well as spherical guest-molecules, including
fullerene (D), its derivative N-methylfulleropyrrolidine (E), and
a snake-like bidentate system consisting of a trinitrodicyanome-
thylenefluorene attached to a C60 moiety (F).
To investigate the effects of the individual chemical inputs, C
and E were added to the receptor system 4 in both the absence
and presence of anions. It was observed that, after addition of 2.0
molar equiv of C (0.8 mM) and 0.5 equiv of E (0.2 mM) to a 0.4
mM CH2Cl2 solution of receptor 4, the color changed from
yellow to brown almost instantaneously on the laboratory time
scale (Scheme 10).
This visual color change was thought to be due to the
formation of the complex C2⊂4, wherein receptor 4 resides in its
1,3-alternate conformation. The absorption spectrum of this
presumed complex displayed CT bands centered at λmax = 525,
720, and 1220 nm (ε = 3700, 2000, and 2800 M−1 cm−1) (cf.
Figure 12a). Addition of 2 equiv of chloride anions to this
solution results in a conformational change of receptor 4 from
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Chemical Reviews
Scheme 8. Initial Suggestion Regarding the Supramolecular Host−Guest Complexation between Receptor 4 and C60
the 1,3-alternate to its cone conformation 4·Cl−. As a
consequence, the 2:1 complex C2⊂4 breaks up and is replaced
by a modified fullerene complex. Initially, the stoichiometry of
this complex was assigned as being 1:2 [i.e., E⊂(4·Cl−)2] as
shown in Scheme 10. Although never reinvestigated in detail,
subsequent studies of C60 binding106 led us to propose that the
species in question is a 1:1 receptor/fullerene complex (Scheme
12).
The anion-induced switching event is readily observed as a
prominent visual color change from brown to green. The
absorption spectra for these species are summarized in Figure
12a. Washing with water removes the chloride anions from the
supramolecular fullerene complex and regenerates the initial 1,3-
alternate conformer. As a result, the complex C2⊂4 is re-
established. This chemical transformation is reflected in an
observable change in the absorption spectrum (Figure 12a).
Addition of a new aliquot of chloride anions to the CH2Cl2 phase
serves to regenerate the green color, as would be expected given
the presumed regeneration of the fullerene complex (cf. Figure
12a). These experiments provide additional support for the
notion that the differential recognition properties of receptor 4
can be controlled by adding or removing chloride anions
(“input”) and that the specific chemical “lead” (i.e., the nature of
the guest) has a demonstrable effect on the optical “output” from
the overall “device” (i.e., the color of the solution).
An interesting binding mode was also demonstrated with the
snake-like trinitrodicyanomethylenefluorene-attached-C60 (F)
derivative. This species contains two different binding motifs, a
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spherical-shaped fullerene head and a nearly planar aromatic
trinitrodicyanomethylenefluorene (TNDCF) tail, and was
designed to interact with 4 through two limiting recognition
modes as shown in Scheme 11. However, subsequent studies of
C60 binding106 led to the suggestion that the dominant species
formed upon substrate binding involves a 1:1 receptor/fullerene
complex (Scheme 13).
The conformationally flexible nature of receptor 4 was used to
follow the complexation of the bifunctional substrate F under
conditions that allow for input-based control. In the presence of
chloride anion, binding of the C60 head is preferred (because of
the presence of the cone conformer of 4 that favors fullerene
binding). In contrast, complexation of the TNDCF tail
dominates in the absence of a chloride anion source. This is
because, in the absence of anions, receptor 4 exists predom-
inantly in the 1,3-alternate conformer, which favors the binding
of planar electron-deficient aromatic guests.
These two binding modes were reflected in (i) the formation
of two different CT complexes and (ii) a change in the optical
signature of the system that could be monitored qualitatively by
the naked eye, by steady-state absorption spectroscopy (Figure
12c), and more quantitatively by time-resolved flash photolysis
studies. Therefore, this system functions as an environmentally
responsive supramolecular switching device, wherein the ON
and OFF states are controlled by the chloride anion
concentration and the effect of switching is “read out” in terms
of the observable changes in the color and spectroscopic
properties.
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Scheme 9. Revised View of the Supramolecular Interactions between Receptor 4 and C60 Involving Stabilization of a 1:1 Complex
as the Dominant Species
Tetraalkylammonium cations can compete with small full-
erenes as substrates for TTF-calix[4]pyrroles. Analyses of this
effect led to an appreciation that small fullerenes bind to TTF-
calix[4]pyrroles with a 1:1 stoichiometry under most conditions,
as opposed to the 2:1 binding stoichiometry initially
proposed.105,107,108 The most detailed study was carried out
using receptors 4 and 5.106 This study included C70 as well as C60
and a number of chloride anion salts. On the basis of both
solution-phase and solid-state structural analyses, it was
concluded that both C60 and C70 are bound within the bowl-
like cup of the anion-complexed cone conformers of these TTF-
calix[4]pyrroles in a ball-and-socket binding mode (Scheme 14
and Figure 13) in the absence of a competing cationic guest. The
binding affinities of receptor 5 for C60 and C70 could be
modulated through the choice of the coordinating anion, namely,
F−, Cl−, and Br−. All three of these anions bind to 4 and 5 and
stabilize the cone conformer of the TTF-calix[4]pyrrole. Thus,
all three act as positive heterotropic allosteric regulators for the
complexation of C60 and C70 by 4 and 5.
However, the specific choice of anion has a strong effect on the
thermodynamic stabilities of the resulting supramolecular
assemblies, as inferred from the fullerene binding constants
recorded in dichloromethane solution. In fact, the selectivity of
receptor 5, that is, whether C60 or C70 was bound preferentially,
was found to be a function of the halide anion used to stabilize the
cone conformer of the TTF-calix[4]pyrroles. Moreover, the
nature of the tetraalkylammonium countercation plays a crucial
role in the binding process of C60 and C70. In particular, smaller
cations, such as tetraethylammonium (TEA+) and, to a lesser
extent, TBA+, compete with the fullerenes for encapsulation
within the host cavity (Figure 13a). As a result, they act as
antagonists for one another. Solid-state findings consistent with
this competition included both an early crystal structure (cf.
Figure 11a) and a number of later X-ray structures of
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calix[4]pyrrole anion complexes (cf. Figure 13a). In retrospect,
it is likely that this competition contributed in part to the original
receptor/fullerene binding stoichiometry being assigned in-
correctly as 2:1.
2.1.4. TTF-Annulated Calix[4]pyrroles and Surface
Studies. Sanguinet and co-workers reported on the self-
assembled monolayer (SAM) systems constructed by mono-
TTF-calix[4]pyrroles, functionalized with an alkane-thiol
anchoring group (10 and 11), for anion sensing on solid-
supported devices.109 The synthetic strategy used to obtain 10
and 11 is outlined in Scheme 15. The two SAMs fabricated using
10 and 11 were designed to permit anion complexation to be
detected by binding-induced changes in the electrochemical
properties of the TTF units. Two monopyrrolo-TTF references
(MPTTF1 and MPTTF2) were also synthesized to act as
controls. A comparison of the surface coverages obtained for the
SAMs prepared from the two model compounds MPTTF1 and
MPTTF2 with those obtained for the SAMs derived from the
TTF calix[4]pyrroles 10 and 11 revealed that the MPTTF model
compounds provided coverages that were almost 3 times higher
[i.e., (1.9 ± 0.2) × 10−10 and (0.7 ± 0.1) × 10−10 mol cm−2 for
MPTTF1 and 10, respectively]. Based on Cory−Pauling−
Koltun (CPK) models, the areas per molecule for MPTTF1 and
10 were estimated to be 49 ± 7 and 79 ± 11 Å2, respectively. On
this basis, it was concluded that the SAMs constructed using the
TTF-calix[4]-pyrroles 10 and 11 were not organized or as well
packed on the monolayer surface as those prepared using the
control MPTTF model compounds.
CV analyses were used to probe the changes in the redox
potentials of the SAMs prepared from compounds 10 and 11,
along with the reference systems, as a function of Cl −
concentration under solution-phase conditions (dichlorome-
thane). Although it was expected that addition of Cl− to the
SAMs derived from the two MPTTF model compounds would
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Figure 11. (a) Single-crystal X-ray structure of 4 and C60 wherein
outside guest binding is seen in the solid state. (This figure was redrawn
using data that were originally published in ref 105.) As detailed in the
text, a 1:1 encapsulated complex is now believed to pertain in solution.
Note that the disordered propyl substituents on the TTF subunits have
been truncated for clarity. (b) Vis−NIR spectra of (i) a 0.135 mM
solution of 4, (ii) a 0.0687 mM solution of C60, (iii) the putative complex
with fullerene produced after the addition of 0.5 equiv of C60 to the
chloride-anion bound form of 4, (iv) a mixture of 4 with 0.5 equiv of C60,
and (v) a mixture of 4 and 0.5 equiv of C60 in the presence of excess
TBACl. All spectroscopic measurements were carried out in CH2Cl2 at
298 K. (Reproduced with permission from ref 105. Copyright 2006
Wiley-VCH Verlag GmbH.)
Table 5. Reduction Potentials of C60 Observed Before and
After the Addition of a Cl− Anion Salt, Receptor 4, and
Receptor 4 in Combination with a Cl− Anion Source at 298 K
in CH2Cl2
entity E11/2 (V) E21/2 (V) ΔE11/2 (V) ΔE21/2 (V)
C60 −1.444 −1.045 − −
C60 + Cl− −1.440 −1.042 +0.004 +0.003
C60 + 4 −1.443 −1.056 +0.001 −0.011
C60⊂(4·Cl−) −1.437 −1.119 +0.007 −0.074
a
All measurements were performed in anhydrous deoxygenated
CH2Cl2 solution, at ambient temperature and under an Ar atmosphere.
The concentration of C60 was 0.2 mM and 0.10 M of TBAPF6 was
added as supporting electrolyte. Cyclic voltammograms were obtained
with a sweep rate of 200 mV s−1. The half-wave potentials E1/2
reported were obtained from an average of the cathodic and anodic
cyclic voltammetric peaks. All potentials are referenced to the
ferrocene/ferrocenium couple (Fc/Fc+)
lead to only minor negative shifts in the first oxidation waves, it
was actually found that the addition of a large amount of Cl− to
the SAMs induced a small but significant positive shift (ΔE1/21 =
+15 mV). This observation, which remains to be explained,
stands in marked contrast to what was seen in the case of the
SAMs derived from 10 and 11. In these cases, the progressive
addition of Cl− (from 0 to 0.5 μm) induced a significant negative
shift (ΔE1/21 ≈ −30 mV) in the first oxidation process (Figure
14). A comparison of the maximum negative shifts induced by
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the addition of Cl− to a solution of the TTF-C[4]P-based system
11 (Δ E1/21 = −170 mV) and to the SAM derived from it (ΔE1/21
= −30 mV) revealed that the Cl−-induced shift was much smaller
in the SAM system than in solution. This observation is ascribed
to the fact that immobilization of the TTF-calix[4]pyrrole
receptor renders more difficult the conformational change from a
1,3-alternate conformation to the cone conformation that is a
known predicate to anion binding. In fact, it is possible that only a
fraction of the immobilized TTF-C[4]Ps have enough free space
to undergo this crucial conformational change and thus act as
anion-binding and signaling sites. Support for this latter notion
came from a close inspection of the cyclic voltammograms
recorded in the presence of Cl−. The cyclic voltammograms
show (Figure 14) that the oxidation and reduction peaks became
broader upon addition of Cl−. Such an observation is consistent
with a system that results from the superposition of two different
redox processes, one corresponding to the first redox process
associated with the uncomplexed TTF-C[4]P 11 and one
corresponding to the complex (i.e., 11·Cl−).
2.1.5. TTF-Annulated Calix[4]pyrroles for Chemores-
ponsive Supramolecular Copolymerization with Hetero-
complementary Calix[4]pyrroles. A new set of artificial self-
assembled materials,110 constructed by mixing two different
heterocomplementary macrocyclic receptors, namely, the
electron-rich TTF-calix[4]pyrroles (4−6) and electron-deficient
bis(dinitrophenyl) meso-substituted calix[4]pyrroles (12 and
13) (Figure 15), was reported by Sessler et al.
The resulting supramolecular polymeric materials, stabilized
by a combination of donor−acceptor-induced π−π-stacking and
hydrogen-bonding interactions, undergo dynamic, reversible
dual-guest-dependent structural transformations upon exposure
to different types of external chemical inputs, namely, Cl− and
TNB. The supramolecular polymerization process and dynamics
of the copolymers along with their analyte-dependent responsive
behavior were established by various spectroscopic techniques.
Most significantly, it was demonstrated that the copolymer
formed from the supramolecular interactions between the
ditopic monomers collapsed to its nonoligomerized species
upon the addition of either Cl− or TNB. Under solution-phase
conditions, dynamic light scattering (DLS) and diffusion-
ordered NMR (DOSY-NMR) spectroscopy were used to
establish the formation of deaggregated species and the
formation of solutions with lower net viscosity, respectively.
Solid-state structural information was obtained for both the
monomeric and polymeric materials.
Sessler and co-workers reported another self-assembled
system111 constructed from 5 and an appropriately chosen
calix[4]pyrrole pyridinium salt, either 15 or 16 (Figure 16).
When the noncoordinating BArF − {tetrakis[bis(3,5-
trifluoromethyl)phenyl]borate} anion salt 15 was used, a linear
supramolecular oligomer was formed upon mixing with 5 in a 1:1
ratio in chloroform. A very different species, a structurally
characterized capsule product, was obtained when the
corresponding iodide salt 16 was used (cf. Figure 16 and
discussion below).
The supramolecular ensembles produced from mixtures of 5
and 15 or 5 and 16 were found to be dependent on the nature of
the salts present in solution, as inferred from studies with
tetraethylammonium tetrakis[bis(3,5-trifluoromethyl)phenyl]-
borate (TEABArF), tetrabutylammonium iodide (TBAI), and
tetraethylammonium iodide (TEAI). In fact, mixtures of 5 and
15 were found to give rise to three different supramolecular
complexes from one parent system, (5·15)n, upon addition of
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Scheme 10. Binding Modes Initially Proposed for Receptor 4 Induced by Different Inputs (A−E) in the Presence and Absence of a
Chloride Anion Source

a
On the basis of subsequent experiments, the binding stoichiometry for the fullerene complex is now considered to be 1:1. See Scheme 12 and ref
106.

Scheme 11. Binding Modes Initially Proposed for the Interaction of Receptor 4 and the Bifunctional Substrate F in the Presence
and Absence of Chloride Anion

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Figure 12. (a,b) UV−vis−NIR spectral changes observed for a
“switching device” based on the TTF-calix[4]pyrrole 4 observed in
the absence and presence of various inputs in CH2Cl2 at room
temperature. (c) Visual effects under ambient conditions. (This figure
was updated based on the findings presented in Schemes 12 and 13. The
original version with errors in complex stoichiometry originally
appeared in ref 107. Copyright 2008 American Chemical Society.)
each of these inputs. The noncoordinating nature of the BArF−
anion means that the addition of the TEA+ cation in the form of
its BArF− salt (TEABArF) to a mixture of 5 and 15 in chloroform
does not trigger any conformational change in either of the two
calix[4]pyrrole units. Therefore, there is no calix[4]pyrrole cavity
into which the TEA+ cation can be encapsulated.
On the other hand, the pyridinium subunits present in the Pyr-
C[4]P dication 15 can “intercalate” into the “clefts” that
characterize the 1,3-alternate form of 5. This results in self-
assembly and the production of a linear aggregate, (5·15)n,
wherein the noncoordinating BArF− anions provide for charge
balance. When TEABArF was replaced by TBAI in the above
studies, the electron-rich BTTF-calix[4]pyrrole 5 underwent a
Scheme 12. Dominant Binding Modes Seen for Receptor 4 Observed with Different Substrates (A−E) and in the Presence and
Absence of a Chloride Anion Source
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conformational switch to give its iodide-bound cone conformer.
Under the experimental conditions employed, the tetrabuty-
lammonium cation was not encapsulated within the bowl-like
cavity of the resulting anion complex, [5·I]−. Instead, it was
calix[4]pyrrole 15 that was bound in a 2:1 capsule-like fashion to
give 15⊂2[5·I]−, as shown in Figure 16.
Sessler and co-workers also reported another short supra-
molecular dynamic oligomeric system.112 This environmentally
responsive material was produced from two heterocomplemen-
tary subunits, namely, glycol diester-linked bis-2,5,7-trinitrodi-
cyanomethylenefluorene-4-carboxylate (TNDCF) and 4. The
underlying interactions are shown schematically in Figure 17.
When both of these components are mixed in organic solvents
(e.g., CHCl3, CH2ClCH2Cl, or methylcyclohexane), supra-
molecular aggregation takes place to produce supramolecular
oligomers, (4·G)n, that are presumably stabilized by hydrogen-
bonding and donor−acceptor-based CT interactions. The
fluorescence emission of the TNDCF subunit is quenched
under conditions that promote the formation of supramolecular
aggregates containing 4 and TNDCF. However, it is restored
when the oligomer is destroyed, leading to the suggestion that
oligomer (4·G)n could act as a dual-analyte chemoresponsive
sensing system. In fact, the combination of quenching and
analyte-induced “turn-on” fluorescence was used to test for
anions and nitroaromatic explosives in initial proof-of-concept
experiments (Figure 17).
To understand further the determinants that control self-
association in calix[4]pyrrole-based systems, Sessler and co-
workers recently reported the results of a study wherein the rigid
calix[4]pyrrole systems 12, 13, 15, and 16 used initially were
replaced by a set of new flexible alkyl-linked bis-dinitrophenyl
esters (i.e., H−J, Figure 18).113
Mixing 4 and any of the esters H−J in chloroform gave rise to
an immediate color change on the laboratory time scale, with the
solution turning from yellow to green. This color change was
accompanied by an increase in the absorbance intensity at 566
nm in the UV−vis−NIR absorption spectrum, a finding
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Scheme 13. Dominant Binding Modes Observed for Receptor 4 and the Bifunctional Substrate F in the Presence and Absence of
Chloride Anion
Scheme 14. Proposed Binding Mode for Receptor 4 and C60
or C70 as Observed in the Presence of Halides and (Inset)
Single-Crystal Structure Showing 1:1 Binding Mode with the
Same Net (TBA)[C60⊂5·F] Stoichiometry as Believed To Be
Operative in Solution
considered diagnostic of a CT interaction and, hence, self-
association between the species. Evidence for stabilizing
hydrogen-bonding interactions and through-space proton-
coupling interactions between 4 and the dinitrophenyl moiety
of the bis-esters came from 1H NMR spectroscopic analyses. X-
ray structures, revealing the presence of linear, self-assembled
polymeric entities in the solid state, provided further support for
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Figure 13. Single-crystal X-ray diffraction structures of (a) [TEA⊂(5·
Cl)], (b) (TOA)[C60⊂(4·Cl)], (c) (TOA)[C70⊂(4·Cl)], and (d)
(THA)[C70⊂(5·Cl)]. For clarity, the C60 and C70 moieties are depicted
as violet and purple space-filling models, respectively. Note: TEA+ =
tetraethylammonium cation, TOA+ = tetraoctylammonium cation, and
THA+ = tetrahexylammonium cation. (This figure was redrawn using
data that were originally published in refs 106 and 110. Copyright 2014
American Chemical Society and 2011 National Academy of Sciences,
respectively.)
the proposal that all three combinations of 4 with H−J gave rise
to self-associated species in chloroform. Dilution-based
absorption spectroscopic measurements carried out in chloro-
form of the self-assembled systems revealed Ka values of 1.5 ×
103, 1.3 × 103, and 3.8 × 103 M−1, respectively, corresponding to
the 1:1 binding constants leading to (4·H)n, (4·I)n, and (4·J)n.
Another supramolecular oligomer constructed by two redox-
responsive heteroditopic monomers, 4 and K, was reported in
2015.114 This more complex system utilizes two different binding
modes, where the carboxylate of [6,6]-phenyl-C61-butyric acid
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Figure 14. Cyclic voltammograms of self-assembled monolayers
prepared from compound 11 measured in dichloromethane (surface
coverage of 11 was estimated to be 0.7 ± 0.1 × 10−10 mol cm−2)
recorded after additions of successive aliquots of TBACl. A Fc/Fc+
reference electrode was employed using 0.1 M TBAPF6 as the
supporting electrolyte. A 0.2 V s−1 scan rate was used. Inset: CV
titration curves showing the negative shift of the first oxidation potential
(measured at the maximum intensity) of 11 seen upon addition of Cl−
ions. (Reproduced with permission from ref 109. Copyright 2009 Wiley-
VCH Verlag GmbH.)
(PCBA) binds through hydrogen bonding to the pyrrole NH
protons of 4 in its cone conformer and the spherical C61 subunit
present in PCBA is bound in the cavity of 4 through CT
interactions. The resulting ensemble could be modulated by
means of chemical and electrochemical stimuli. Addition of an
organic base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, DBU)
initiates self-assembly of the monomers through a molecular
switching event. The resulting supramolecular ensemble could
Scheme 15. Synthetic Route to TTF-Calix[4]pyrroles with Alkanethiol Anchoring Groups Used to Prepare SAMs
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be disaggregated through the addition of an organic acid (e.g.,
methanesulfonic acid, MSA) or electrolysis (Figure 19). A
noteworthy feature of this system is that it can be controlled
through the use of highly orthogonal inputs, namely, chemical
and electrochemical, which leads to the suggestion that more
complex systems, such as this one, might have a role to play in the
creation of stimulus-responsive systems where external factors
are used to modulate the structure and function of self-assembled
materials over a range of length scales.
2.1.6. TTF-Annulated Calix[4]pyrroles for Ion-Medi-
ated Reversible Electron-Transfer (ET) Process in Supra-
molecular Ensembles Formed with Electron-Deficient
Guests. Anion-mediated reversible ET in a synthetic host−guest
assembly that mimics aspects of cofactor-controlled biological
electron transfer was reported in 2010 by Sessler and co-
workers.115 As with other calix[4]pyrrole ensembles, anion
binding to 4 in this instance produces a cone conformer that can
act as a receptor for large cationic guests, namely, the electron-
deficient benzimidazolium quinone (BIQ2+). The resulting
complex undergoes intraensemble thermal electron transfer to
produce a long-lived charge-separated (CS) state. Based on X-ray
structural analysis, this supramolecular capsule is best described
as a tightly coupled biradical species, [4]2•+·BIQ•+·2Cl−, wherein
two cone-like anion-bound conformers of 4 (one of which is
oxidized by one electron) serve to encapsulate one BIQ•+ guest
(Figure 20).
As noted above, anion binding to 4 triggers conversion to the
cone conformer and favors forward ET to the BIQ2+ acceptor. In
contrast, the addition of a tetraethylammonium cation source,
which serves to compete for the “pocket” of 4·Cl−, leads to
electron back-transfer from BIQ•+ to 4•+. This restores the initial
oxidation states of the donor−acceptor pair (Figure 21). This
type of ON−OFF switchable ET behavior can be observed by
monitoring the changes in absorption intensity at 751 and 1995
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Figure 15. Schematic representation of the supramolecular self-assembly between the TTF-calix[4]pyrroles 4, 5, and 6 and the heterocomplementary
dinitrophenyl-calix[4]pyrroles (DNP-C[4]P) 12 and 13. Chemoresponsive behavior is seen upon the addition of either TEACl or TNB. (Reproduced
with permission from ref 110. Copyright 2011 National Academy of Sciences.)
Figure 16. Schematic representation of three limiting equilibrium states
that can be produced from 5 and 15 depending on the nature of the
experimental conditions employed. In the absence of a coordinating
anion or competing cation source, the self-assembled oligomer (5·15)n
is obtained in CHCl3. Changes in this oligomer can be triggered by the
addition of various tetraalkylammonium salts. (Reproduced with
permission from ref 111. Copyright 2013 American Chemical Society.)
nm in the steady-state absorption spectra, as well as by electron
paramagnetic resonance (EPR) spectroscopy (Figure 22).
Another supramolecular complex involving host system 4 that
undergoes ground-state ET was reported in 2011.116 This system
was constructed using Li+@C60, a species that, like BIQ2+, is
complexed by the anion-bound cone conformer of 4. Compared
to pristine C60, Li+@C60 is a more powerful electron acceptor.117
This makes it a more promising candidate for ground-state ET
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from receptor 4 than the native fullerene. After treating host 4
with Li+@C60 and a Cl− anion source in the absence of a
competing cation, ET is switched ON to produce a 1:1 radical ion
pair between 4•+ and [Li+@C60]•− with a net stoichiometry of
Li+@C60⊂4·Cl−. Addition of tetraethylammonium chloride
provides a source of TEA+, a species that acts as a competitive
inhibitor for the neutral Li+@C60•− ET product and its cationic
precursor, Li+@C60. As a consequence, these fullerene species are
released from the calix[4]pyrrole cavity, resulting in electron
back-transfer and restoration of the initial donor and acceptor
pair. Evidence in support of these conclusions is summarized
briefly below.
The appearance of an absorption band at 1035 nm upon the
gradual addition of tetra-n-hexylammonium chloride (THACl)
to a benzonitrile solution of 4 and Li+@C60 is ascribed to the
generation of the one-electron-reduced species [Li+@C60]•−, as
shown in Figure 23a. The intensity of this peak gradually
increases upon the addition of THACl until it reaches a constant
value, at which point the ET process is considered essentially
complete. Upon addition of TEACl to this supramolecular ion-
pair system, Li+@C60•−⊂4•+·Cl−, the absorbance feature at 1035
nm gradually decreases in intensity, a finding consistent with the
breakup of the radical-ion-pair complex and generation of the
new supramolecular system TEA+⊂4·Cl−.
Further evidence for the formation of a radical-ion-pair
complex came from EPR analyses of the species produced after
the proposed ET from 4 to Li+@C60. When the spectrum was
recorded in benzonitrile at 298 K (Figure 23b), a four-line signal
was observed. This signal was ascribed to a 4•+·Cl− radical cation,
in which the electron spin is localized on only one TTF unit,
rather than delocalized throughout a π-dimer radical-cation
complex involving another TTF unit. The signal at g = 4.43
(Figure 23c) was attributed to the interaction between the two
unpaired electrons, which generates a triplet state. A single-
crystal structure of the proposed radical ion pair was obtained; it
is shown in Figure 24a,b.
Subsequently, an example of photoinduced electron transfer
(PET) from an electron-rich TTF-calix[4]pyrrole, 5, to a
porphyrin carboxylate, PA, within a supramolecular ensemble
was reported.118 A carboxylate moiety was chosen as the anion
moiety in constructing the proposed supramolecular complex
involving 5 and PA because carboxylate anions are known to bind
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Figure 17. Graphical representation of the proposed supramolecular ensemble formed from 4 and TNDCF (G) and schematic view of the breakup of
the supramolecular oligomer that occurs upon exposure to TNB (left) or a chloride anion source (right). In both cases, fluorophore G is released.
(Reproduced with permission from ref 112. Copyright 2016 Wiley-VCH Verlag GmbH.)
to the NH protons of the calix[4]pyrroles in a 1:1 fashion and to
induce a conformational change from the 1,3-alternate to the
cone conformer in analogy to what is seen in the case of the
chloride anion. In fact, the PA anion (TEA+ countercation) was
found to bind to 5 with a 1:1 stoichiometry (Figure 25a) and a
binding constant of 6.3 × 104 M−1 at 298 K in benzonitrile.
In initial studies, TEA+ was chosen as the countercation to the
carboxylate moiety, as it is known to bind strongly inside the
bowl-shaped cavity of the cone conformer of TTF-calix[4]-
pyrroles.106 This dual binding to receptor 5, involving both TEA+
and the carboxylate moiety, was expected to enhance the
interaction between the porphyrin PA and 5, leading to stronger
supramolecular complexation. Laser photoexcitation of this
supramolecular complex resulted in the formation of the triplet
charge-separated state composed of a TTF•+ radical cation and
the radical anion PA•−. The rate constants corresponding to the
forward and backward intramolecular electron transfer within the
ensemble were determined to be 2.1 × 104 and 3.6 × 102 s−1,
respectively. The rate constants of intermolecular forward and
backward electron transfer occurring in the absence of complex
formation were also determined and found to be 4.4 × 108 and
9.8 × 108 M−1 s−1, respectively.
A rare example of a three-component supramolecular
ensemble undergoing PET was also reported (Figure 25b).119
In this case, Li+@C60 was used in conjunction with 5 and a
different porphyrin carboxylate anion, PA2. Photoexcitation of
the three-component mixture resulted in PET from the triplet
excited state of PA2 to 5•+. This produced a higher-energy
charge-separated state that was proposed to consist of the
supramolecular radical ion complex Li+@C60•−⊂5·PA2•+, which
decays to the ground state with a lifetime of 4.8 μs. A
characteristic signal at 1035 nm in the vis−NIR absorption
spectra (Figure 26a) is consistent with the formation of a charge-
separated species, 5•+/Li+@C60•−, where the PA2 is in its neutral
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form. The sum total of the findings provides support that the
three components assemble to produce a multicomponent
redox-active ensemble.
2.2. TTF-Annulated Hybrid Calix[n]pyrrole Systems
2.2.1. “Pacman”-Type Schiff-Base TTF-Calix[4]pyrrole.
A very different class of flexible TTF-pyrrole-derived macrocyclic
molecular receptor is the Schiff-base system 17, reported by
Sessler and co-workers.120 This so-called Pacman receptor
system combines the complexation and physiochemical proper-
ties of the benzoannulated-TTF pyrrole (BTTF-pyrrole) used to
construct 5 with the synthetic versatility and simplicity of Schiff-
base condensation procedures. The flexible framework of the
Pacman receptor and its Schiff-base construction is thought to
underlie its ability to stabilize a number of metal complexes. The
synthetic route leading to 17 is summarized in Scheme 16. Its
metal complexation chemistry is discussed below.
Receptor 17 was found to react with a Pd(II) source to
produce a bimetallic complex 17·Pd2. The formation of this
complex was found to help in the stabilization upon oxidation of
an otherwise difficult-to-access mixed-valence TTF radical
dimer. EPR and optical spectroscopies were used to characterize
the mixed-valence species. The crystal structure of complex 17·
Pd2 supports its Pacman-like structure (Figure 27).
Sessler and co-workers also reported a TTF-based macrocyclic
host system, the TTF-calix[2]pyrrole[2]thiophene 18,121 which
can bind electron-deficient planar guest molecules in a Pacman-
like fashion. The system acts as a chemosensor in that a readily
visible color change is produced in the presence of nitro-
aromatics, such as TNB and TNP. The color presumably reflects
formation of a D−A-type complex that is stabilized as the result
of π−π donor−acceptor interactions. The synthesis of 18 is
outlined in Scheme 17.
Solid-state structural analysis of this host−guest supra-
molecular system by single-crystal X-ray diffraction established
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Figure 18. Single-crystal X-ray structure of the proposed supra-
molecular assembly formed when 4 and the bis-dinitrophenyl esters H−
J are mixed in noncompetitive organic media. (Reproduced with
permission from ref 113. Copyright 2014 Royal Society of Chemistry.)
a “cleft-like” arrangement wherein the two TTF units lie parallel
to one another and are separated by approximately 3.44−3.56 Å.
The structure in question is shown in Figure 28. This distance
allows for the formation of Pacman-type sandwich complexes
with planar electron-deficient guest molecules.
2.2.2. TTF-Annulated Calix[2]pyrrole[2]thiophene. In
work that bears some analogy to that discussed above, Jeppesen
and co-workers reported a rare example of a TTF-calix[2]-
pyrrole[2]thiophene hybrid system, 19, wherein two thiophene
moieties are incorporated within the central macrocyclic skeleton
(Scheme 18).122
Keeping with the analogy between 18 and 19, the latter system
was found to act as a molecular receptor for TCNQ, which was
bound in a Pacman-like arrangement. The guest-binding ability
of 19 was supported by single-crystal X-ray diffraction studies
(Figure 29). On the basis of this structure, guest binding is
stabilized by CT interactions and overlap of the π-surfaces of the
two TTF side arms with the electron-deficient TCNQ.
Support for the presence of CT interactions came from UV−
vis−NIR spectroscopic studies, as well as EPR studies using
CH2Cl2 as the solvent. Neither 19 nor TCNQ gives rise to
significant absorption features beyond 700 nm. However, upon
mixing of these components, two newly generated CT bands
appear at λmax = 749 and 851 nm. These optical features are
characteristic of a TTF-to-TCNQ CT interaction. The EPR
spectrum also revealed the presence of a weak radical signal
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centered at g = 2.010, which is in the region expected for both a
TTF radical cation and a TCNQ radical anion.
2.3. TTF-Annulated Expanded Calix[n]pyrroles
In 2012, Sessler and co-workers reported the synthesis of several
expanded calix[n]pyrroles (n = 5 and 6) containing a higher
number of TTF-pyrroles (compounds 20−22; Scheme 19).123
These systems were of intrinsic interest since they have the same
empirical formula as their known tetrakis-TTF-calix[4]pyrrole
analogues (i.e., 4 and 5), but were expected to display different
conformational features and to have larger cavity sizes. These
new congeners of 4 and 5 were synthesized using the same acid-
catalyzed condensation reaction conditions95,97,98 originally
developed to obtain the TTF-calix[4]pyrrole products. Interest-
ingly, when BTTF-pyrrole was used as a precursor, the expanded
calix[n]pyrroles 20 and 21 were produced, along with 5, in good
to moderate yields. In contrast, when the analogous reaction was
carried out with PrS-TTF-pyrrole, the isolated products
consisted of 4 and 22, with only a trace amount of the putative
hexakis derivative being observed in the matrix-assisted laser
desorption ionization time-of-flight (MALDI-TOF) mass
spectrum of the crude reaction mixture.
Single crystals of the benzo-fused calix[n]pyrrole products 5,
20, and 21 suitable for X-ray diffraction analysis were obtained in
the form of the corresponding chloride anion complexes (as the
TBA+ salts). The resulting structures allowed direct visualization
of the three-dimensional arrangement of the TTF units on the
periphery of each macrocyclic core in the solid state (Figure 30).
It also allowed some inferences about the anion-binding features
to be drawn.
Within the series consisting of 5, 20, and 21, 1:1 chloride anion
complexes are seen in the solid state. In the case of receptor 21,
all six pyrrolic protons interact with the bound chloride, as
inferred from the structural parameters (Cl···H−N distances of
2.39 ± 0.01 Å). The Cl− anion is centered in the cavity and
resides within an imaginary plane defined by the hexagonal
arrangement of the pyrrolic nitrogen atoms. In contrast, four
NH···Cl− hydrogen-bonding interactions were seen in the case of
receptors 5 and 20, as judged from the Cl···HN distances (2.49 ±
0.07 Å for 5 and 2.43 ± 0.01 Å for 20). On this basis, it was
concluded that receptors 5 and 20 are not as optimized for Cl−
binding as 21.
Analysis of the binding isotherms obtained from UV−vis
spectroscopic titrations carried out in CHCl3 in the presence of
both anionic (Cl−, Br−, I−, MeCO2−, H2PO4−, and HSO4−, as the
TBA+ salts) and neutral (TNB and TNT) substrates revealed
that the hexpyrrolic system 21 is the most efficient molecular
receptor for anions (e.g., Ka = 5.3 × 106 M−1 in the case of Cl− as
its TBA+ salt; see Table 6). In contrast, compound 5 proved most
effective for the recognition of electron-deficient nitroaromatic
explosives, such as TNB and TNT (e.g., Ka = 1.7 × 104 M−1 in the
case of TNB). The relatively high anion affinities of 21 were
ascribed to the size matching revealed in the structural analysis
discussed above, as well as the presence of six presumably
preorganized NH···X− hydrogen-bonding interactions. The fact
that 5 was the best receptor in the series for both TNB and TNT
was rationalized in terms of the TTF substituents being able to
adopt conformations suitable for “sandwich-type” substrate
recognition through D−A interactions, as well as the attendant
cooperative effects seen for planar electron-deficient substrates in
the case of the TTF-calix[4]pyrroles discussed above. Both of
these effects rely on an ability to access well-defined 1,3-alternate
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Figure 19. (a,b) Chemical structures of the heteroditopic monomers (a) 4 and (b) K. (c) Illustrations of an anion-bound form of the 4 and the phenyl
C61 butyric acid (PCBA, K). (d) Schematic representation of the self-assembled structure produced from the cone conformer of 4 and the deprotonated
form of K. Also shown is an approach for controlling this system through acid−base chemistry and electrochemical oxidation. (Reproduced with
permission from ref 114. Copyright 2015 American Chemical Society.)
Figure 20. X-ray crystal structure of the Cl−-induced supramolecular
radical-ion-pair capsule constructed by 4 and BIQ2+ of net stoichiometry
[4]2•+·[BIQ] •+·2Cl−. (Reproduced with permission from ref 115.
Copyright 2010 American Association for the Advancement of Science.)
molecular conformations, something that is possible only for 5
within this congeneric series.
2.4. TTF-Annulated Porphyrins
2.4.1. TTF-Porphyrins with Different Numbers of Fused
TTF Units. As mentioned earlier, TTF-annulated pyrroles
function as good electron-donor units when incorporated into
anion-binding motifs such as calix[n]pyrroles. In a view of their
intriguing redox properties, TTF-pyrroles are also attractive
building blocks for preparing π-conjugated oligopyrrolic macro-
cyclic systems (e.g., porphyrins and expanded porphyrins) that
might act as photo- or redox-active chromophores. Unlike TTF-
annulated calix[n]pyrroles, these TTF-porphyrin analogues
would be expected to form stable metal complexes, which
might allow their intrinsic photophysical and electrochemical
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properties to be further tuned. Axial ligand coordination to the
metal center might provide an additional specific approach to
modulating the features of these systems. These possibilities
make the marriage of TTF and porphyrin chemistry attractive; it
might offer a range of potential supramolecular D−A systems
useful for a variety of prospective applications.
One way to incorporate TTF into conjugated pyrrolic
frameworks would be through direct or stepwise condensation
with suitable aryl aldehydes. In fact, using these and related
approaches, a number of TTF-annulated porphyrins, specifically
23−31, containing differing numbers of fused TTF units have
been prepared.124−127 Their chemical structures are shown in
Chart 3. These systems are discussed further below.
In some cases, a simple and straightforward acid-catalyzed
macrocyclization protocol involving the condensation of a TTF-
annulated pyrrole with an electron-deficient aldehyde under
dilute conditions results in the effective formation of TTF-
functionalized porphyrin derivatives. In fact, this approach was
used to prepare compounds 28−31. However, to synthesize
mono- and bis-TTF-annulated porphyrin derivatives (23−26),
functionalization of the TTF-annulated pyrroles or other
precursors proved necessary prior to carrying out the final
macrocyclization reaction. Typically, this functionalization has
taken the form of creating either activated pyrroles or di- or
tripyrrolic precursors. For instance, condensation of TTF-
pyrrole bis-carbinol (TTFPBIOL) with a tripyrrane (TP2 or
TTFTP) was used to synthesize 23 and 26, whereas
condensation of a TTF-pyrrole with pyrrole bis-carbinol
(PBIOL) was used to prepare 25. The tris-TTF-porphyrin
(30) was obtained through the condensation of a TTF-pyrrole
with an aldehyde precursor while controlling the molar ratios;
subsequent careful purification by column chromatography
yielded the desired product. The synthetic routes used to obtain
representative TTF-porphyrins are summarized in Scheme 20.
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Figure 21. Chemical structures of the molecules, ions, and self-assembled structures associated with the proposed supramolecular ion-mediated ET
process involving receptor 4 and BIQ2+. (Reproduced with permission from ref 115. Copyright 2010 American Association for the Advancement of
Science.)

Figure 22. (a) Results of a UV−vis−NIR spectroscopic titration wherein 4 (30 mM) and 1 molar equiv of BIQ2+2PF6− were treated with increasing
quantities (up to 10 equiv) of THACl in CHCl3. (Inset) EPR spectra of a 1:1 mixture of 4 and BIQ2+2PF6− (1.1 × 10−4 M in each) recorded in CHCl3 at
room temperature upon the gradual addition of increasing quantities of THACl. (b) Cation-induced reverse ET seen upon the addition of up to 15 equiv
of TEACl to a 1:1 solution of 4 and BIQ2+2Cl− (30 mM in each). (Inset) EPR spectra of a 1:1 mixture of 4 and BIQ2+2Cl− (1.1 × 10−4 M in each)
recorded in CHCl3 at room temperature upon the addition of up to 5 molar equiv of TEACl. (Reproduced with permission from ref 115. Copyright 2010
American Association for the Advancement of Science.)

A single-crystal X-ray diffraction analysis of 26 revealed that
the annulated porphyrin adopts a nonplanar saddle-like
conformation in the solid state (Figure 31a,b). The distortion
from planarity was thought to reflect the presence of the bulky
peripheral substituents126,128−132 (viz., four ethyl groups at β-
positions of the pyrroles and four adjacent phenyl groups at the
meso positions) and the steric clashes they would impose were
the macrocycle to adopt a more planar arrangement.
The free-base and zinc(II) complexes, 31-H2 and 31-Zn, also
proved amenable to X-ray diffraction structural analysis. These
analyses revealed only modest deviations from ring planarity as
compared to what was seen in the case of 26. Moreover, the
meso-pentafluorophenyl groups of 31-H2 and 31-Zn were found
to lie almost perpendicular to the mean porphyrin planes (cf.
Figure 31c−f). The differing structural effects seen for 31-H2 and
31-Zn relative to 26 were rationalized in steric terms.
TTF-annulated porphyrins have attracted interest because of
the possibility that they might display intramolecular donor−
acceptor effects in either the ground or excited state. The
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absorption spectra of most TTF-annulated porphyrins prepared
to date reveal spectral features typical of native porphyrins
(Figure 32). However, in some cases, a near-IR (NIR) absorption
is seen that is broad and weak and is thought to originate from a
transfer of charge from the TTF subunit(s) to the central
porphyrin. Based on DFT calculations, molecular orbital (MO)
diagrams of the singly substituted derivatives 28-H2 and 28-Zn
were constructed. Analysis of these orbitals revealed that the
HOMO is predominantly concentrated on the TTF unit,
whereas the LUMO is centered primarily on the macrocyclic
core (Figure 33). This prediction lends credence to the notion
that an intramolecular CT phenomenon might be observed upon
photoexcitation. Calculations also revealed that the energetically
degenerate HOMO − 1 and HOMO − 2 represent what are
essentially paired symmetric combinations (a1u and a2u) of the
porphyrin-centered MOs. The degenerate LUMO and LUMO +
1 were also predicted to be composed primarily from porphyrinic
MOs with eg symmetry. The observed porphyrin-like optical
properties seen for test TTF-porphyrins, such as a strong Soret
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Figure 25. Schematic representation of photoinduced electron transfer

proposed to occur within supramolecular ensembles formed from the
Figure 23. (a) Near-IR absorption spectral changes that are taken as
electron-rich TTF-calix[4]pyrrole 5 and electron-deficient porphyrin
evidence of ET from 4 (5.0 × 10−5 M) to Li+@C60 (5.0 × 10−5 M) that
carboxylate salts. (a) PET from electron-rich 5 to PA. (b) Dual PET
occurs when THACl is added to a benzonitrile solution of the
from both 5 and PA2 to electron-deficient Li+@C60.
components in question. (b) EPR spectrum (benzonitrile at 298 K) of
the radical ion pair Li+@C60•−⊂4•+·Cl− generated as the result of ET
from 4 (5.0 × 10−5 M) to Li+@C60 (5.0 × 10−5 M) in the presence of
THACl (3.0 × 10−4 M). (c) EPR spectrum of the radical ion pair Li+@
C60•−⊂4•+·Cl− recorded at 77 K. (d) Expanded view of the magnetic
field region highlighted by the red rectangular frame in panel c.
(Reproduced with permission from ref 116. Copyright 2011 American
Chemical Society.)

Figure 24. X-ray structure of the supramolecular complex with a net

stoichiometry of Li+@C60⊂4·Cl−: (a) side view and (b) bottom view.
(Reproduced with permission from ref 116. Copyright 2011 American
Chemical Society.)

band and weaker Q-bands, could thus be rationalized using a

typical Gouterman four-orbital treatment.133,134
Incremental synthetic addition of TTF units to the porphyrin
core produces a monotonic red shift in the absorption bands and
a decrease in the molar absorption coefficient associated with
these transitions (see Table 7). These changes were rationalized
in terms of enhanced intramolecular CT effects. The presence of
four electron-deficient pentafluorophenyl groups (attached to
the meso positions of the porphyrin cores in the cases of 28−31)
serves to enhance this intrinsic CT character (vide infra). In the
presence of electron-rich TTF substituents, the electron-
deficient pentafluorophenyl groups are thought to play an
important role in regulating the observed intramolecular charge-
transfer events. On the other hand Zn2+ metalation does not
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Figure 26. (a) Vis−NIR spectral changes consistent with electron
transfer from 5 (100 mM) to Li+@C60 (100 mM) as seen in the presence
of increasing concentrations of PA2 in benzonitrile. Inset: Expanded
view of the absorption spectrum over the 600−1600 nm spectral region.
(b) Plots of absorbance at 1035 and 680 nm vs concentration of PA2.
(Reproduced with permission from ref 119. Copyright 2015 Royal
Society of Chemistry.)
significantly affect the position or intensity of the intramolecular
CT (ICT) transitions.127
Relative to unsubstituted tetraphenylporphyrin (TPP), an
enormous quenching of the fluorescence (greater than ∼90%)
was seen for most test TTF-porphyrins. Such findings are fully
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Scheme 16. Synthesis of a Schiff-Base TTF-Calix[4]pyrrole
Receptor and Its Bimetallic Pd(II) Complex
Figure 27. Solid-state structure of the Pd(II) complex of a TTF-Schiff-
base calix[4]pyrrole (17·Pd2) viewed along the crystallographic (a) a
axis and (b) c axis. (This figure was redrawn using data that were
originally published in ref 120.)
Scheme 17. Synthetic Route Leading to a TTF-
Calix[2]pyrrole[2]thiophene Receptor
Figure 28. Solid-state structures of the bis-TTF-calix[2]pyrrole[2]-
thiophene 18, showing a Pacman-like binding mode with a bound TNB
guest: (a) side view and (b) top view. (This figure was redrawn using
data that were originally published in ref 121.)
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consistent with intramolecular electron transfer. When the TTF
units of 23 and 24 were oxidized by chemical means (e.g., FeCl3),
the emission was (partly) regenerated relative to a comparable
porphyrin control. The excited-state dynamics of the TTF
porphyrins 28−31 were probed using femtosecond transient
absorption (fs-TA) spectroscopy; these studies were carried out
for both the free-base and Zn2+-complexed forms and revealed
that all of the TTF-porphyrins subject to study were
characterized by excited-state lifetimes falling within the
picosecond time scale. These findings were rationalized in
terms of photoinduced charge separation followed by very fast
charge recombination, which serves to generate the ground-state
species. A summary of the photophysical properties of
representative TTF-annulated porphyrins, along with those of
a reference TPP system, is provided in Table 7.
The fusion of TTF units to the periphery of a porphyrin core
can have a significant effect on the driving force for charge-
separation processes. To assess the underlying redox potentials
that were expected to define the thermodynamics of photo-
induced and thermal ET, square-wave voltammetry (SWV)
analyses were used for many TTF-annulated porphyrins.135
Typically, the characteristic redox signals associated with the
production of the TTF radical cation (TTF•+) and dication
(TTF2+) are observed at relatively low potentials (Table 8).
These potentials vary with structure. Moreover, it was found that
the molecular symmetry of the TTF-annulated porphyrins (e.g.,
28−31) has an influence on the electrochemical behavior, as
reflected in the peak patterns observed in the TTF oxidative
region (cf. Figure 34 and Table 8).
The monosubstituted congeners 28 show two redox waves for
oxidation and reduction. In the case of the trans-orientated bis-
TTF-porphyrin 26, redox patterns similar to those in 28 were
seen. This congruence led to the suggestion that, in 26, little
intramolecular interaction exists between the two TTF units in
the singly oxidized form (i.e., 26•+). In the case of the bis-TTF
porphyrin 29-H2, upon oxidation, complicated oxidative waves
are seen in the SWV results. Although 26 and 29 were not
analyzed under identical conditions, this difference is never-
theless considered to be consistent with the two TTF units
present in 29 being able to communicate electronically through
the intervening porphyrin core.
Similar complexity was seen in the higher derivatives of 30-H2.
A regular positive shift in the reduction signals (Figure 34a) was
also observed in the case of the free-base derivatives as the
number of TTF subunits attached to the porphyrin core
increased.127 These findings were ascribed to an electronic
overlap effect, rather than steric factors.
After metalation, electronic communication between the
separate TTF units becomes restricted, and the individual TTF
sites act as separate redox centers under conditions of oxidation.
Thus, for the zinc(II) complexes, only two signals, corresponding
to TTF•+ and TTF2+, are observed in the oxidative region
(Figure 34b).
Compound 32 is another TTF-annulated porphyrin. It was
synthesized with a view toward exploring whether deaggregation
could be achieved by metal−ligand coordination within a
donor−acceptor-based hybrid supramolecule.136 In dimethyl
sulfoxide (DMSO)/D2O solution, porphyrin 32 exhibits
appreciable aggregation (due to the presence of phenolic −OH
groups at the periphery) and gives rise to spherical particulate
morphologies, as inferred from scanning electron microscopy
(SEM) studies (Figure 35). Axial coordination of an imidazole-
functionalized-fullerene (C60Im) guest to the zinc(II) center of
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Scheme 18. Synthetic Route Used to Obtain a Pacman-Style Calix[2]pyrrole[2]thiophene Receptor System
Figure 29. Solid-state structures of the bis-TTF-calix[2]pyrrole[2]-
thiophene 19 in its uncomplexed “free” state and after TCNQ binding.
The electron-deficient TCNQ guest is bound in a Pacman-like binding
mode and presumably stabilized by donor−acceptor interactions
involving the TTF “arms” of the receptor. Residual solvent and one of
the TCNQ molecules are deleted for clarity. Views along the
crystallographic (a) a axis and (b) b axis. (This figure was redrawn
using data that were originally published in ref 122.)
32 leads to attenuation of the intermolecular aggregation effects
(Figure 36).
Detailed theoretical calculations involving 32 and its supra-
molecular complex 32·C60Im provided insights into their
geometry and electronic nature. As shown in Figure 37a,b, the
HOMO of 32 is mainly localized on the TTF subunits with weak
contributions from the porphyrin π-system; however, the
LUMO is predominately concentrated on the macrocyclic
core. In complex 32·C60Im, the HOMO is located mainly on
the TTF substituents, whereas the LUMO is all but completely
localized on the fullerene group (Figure 37c,d). On this basis,
photoinduced ET from the TTF subunits to the C60 moiety
would be expected.
Ultrafast intrasupramolecular photoinduced charge separation
between the TTF units and the ligated fullerene was established
in 32·C60Im by means of emission and transient absorption
spectroscopic techniques. These studies revealed that the rate
constants for charge separation (kCS) and charge recombination
(kCR) were 1.4 × 1011 and 2.5 × 106 s−1, respectively. The lower
kCR value was taken as an indication of charge stabilization within
the assembled donor−acceptor conjugate; this was ascribed to an
electron-transfer−hole-transfer mechanism.
2.4.2. Quinoxaline-Fused TTF-Porphyrins. A series of
pyrazine-bridged TTF-annulated porphyrins, 33a−c and 34a−
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c,137,138 was reported recently. These systems were obtained in
exceptionally high yield (70−96%) using a procedure that
involved as its key step the nucleophilic substitution of an
aromatic ortho-diamine with a β-diketo-substituted porphyrin (L
or M). It was found that condensation of porphyrin L with
TTFDA gave 33a−c (Scheme 21A), whereas reaction between
porphyrin M and TTFTA, a TTF-tetraamine counterpart,
yielded the TTF-annulated triad 34a−c (Scheme 21B).
As proved true for the directly annulated TTF-porphyrins
discussed above (e.g., 23), the fluorescence intensity and lifetime
of the TTF-pyrazino-porphyrin 33a were decreased relative to
those of a simple porphyrinic control. This reduction was
ascribed to photoinduced electron transfer (PET) from the TTF
unit to the porphyrin core when the system was subjected to
photoexcitation. The fluorescence intensity of 33a increased
upon addition of the chemical oxidant Fe(ClO4)3. Presumably,
this produces an oxidized TTF unit that is a less effective redox
partner for PET. Treatment with a mild reductant restored the
initial, less fluorescent state.
Chemical oxidation of 33a with less than 1 equiv of
[Fe(bpy)3](PF6)3 (where bpy = 2,2′-bipyridine) was found to
lead to a concentration-dependent decrease in the intensity of
the absorption band at ca. 600 nm and the concomitant
emergence of a new broad absorption band peaking at 830 nm,
characteristic of a TTF radical cation (TTF•+) (Figure 38a). The
Soret band was bathochromically shifted while becoming sharper
and more intense. All of these observations led to the suggestion
that the influence of the porphyrin is minor during the first
oxidation process, which occurs mainly on the TTF unit. When
33a was treated with ≥1.4 equiv of [Fe(bpy)3](PF6)3 (Figure
38b), the TTF radical absorption band decreased, and broad
absorption bands in the 600−1000-nm region emerged. A
decrease in the intensity of the Soret band was also seen. These
changes are attributed to the formation of a porphyrin radical
cation. The porphyrin was thus considered to be intimately
involved in the second electrochemical process. Electrochemical
data for representative quinoxaline-fused TTF-porphyrins are
provided in Table 9.
Photoinduced electron transfer (PET) can be induced readily
within the supramolecular complex formed by treating dyad 33b
with a pyridine-appended C60 derivative, C60Py (Figure 39).
Initial evidence for the PET process came from state emission
studies carried out in o-dichlorobenzene, and a gradual
quenching of the fluorescence intensity of 33b at 640 nm was
found upon treatment with C60Py (Figure 40). This quenching is
ascribed to the formation of a singlet excited species, 33b*, that
then undergoes photoinduced electron transfer to the C60Py
acceptor. A binding constant corresponding to the formation of
the supramolecular complex deemed predicative to PET was
obtained from a Benesi−Hildebrand plot constructed from the
fluorescence titration data. The value derived in this way (7.20 ×
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Scheme 19. Synthesis of Expanded TTF-Calix[n]pyrroles

Table 6. Effective Association Constants (Ka, M−1)

Corresponding to the Interaction between the BTTF-
Calix[n]pyrroles (Compounds 5, 20, and 21) with
Nitroaromatic (TNB and TNT) Guests and the TBA+ Salts of
Selected Anions
5 20 21
Cl− 520000 13000 5300000
Br− 21000 8300 34000
I− 480 ndb 1800
MeCOO− 140000 22000 870000
H2PO4− 100000 14000 110000
HSO4− 140 2650 7000
TNB 2800, 17000c 870 1200
TNT 570, 2600c 220 480
a
All Ka values were obtained from UV−vis spectroscopic titration
experiments carried out in CHCl3 at 296 K. The receptor/substrate
binding stoichiometries are either 1:1 or 1:2 (when one or two Ka
values are listed), and were determined on the basis of curve fits or
continuous-variation (Job) plots. The anions were studied in the form
of their tetrabutylammonium (TBA+) salts. The estimated errors are
≤15%. bNot determined. cData from ref 95.
Figure 30. Crystal structures of the chloride anion complexes of a set of
congeneric BTTF-calix[n]pyrroles (where n = 4, 5, and 6): (a) 5, (b) 20,
and (c) 21. The tetraalkylammonium counterions are omitted for
104 M−1 for studies in o-dichlorobenzene) proved remarkably clarity. (This figure was redrawn using data that were originally
high. published in ref 123.)
Evidence of a charge-separated state being formed following
photoexcitation of the supramolecular triad 33b·C60Py came 2.4.3. TTF-Annulated Expanded Porphyrins. Expanded
from femtosecond transient absorption spectral studies. TTF-porphyrins, such as the [28]TTF-hexaphyrin, 35, were
Increases in the absorbance intensity at 1000 nm due to the prepared by methods used to prepare conjugated oligopyrroles
C60Py•− radical anion and at 620−700 nm due to the radical lacking annulated TTF subunits (cf. Scheme 22).139 System 35
cation 33b•+ were observed with time. The electron-transfer was found to undergo PET reactions that could be controlled
complex (charge-separated state) was estimated to have a through a unique process involving conformational switching of
relatively long lifetime (385 ps) in toluene. the hexaphyrin core between Hückel figure-of-eight (35-H) and
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Chart 3. Structural Formulas of Various TTF-Porphyrins and Model Porphyrins
Möbius-twisted (35-M) conformers. This finding provides a
complement to recent studies designed to probe the limits of
Möbius aromaticity, where more classic expanded porphyrins
have played a prominent role.140−142 As a general rule, large
meso-substituted expanded porphyrins can adopt a variety of
conformations, with several of the well-characterized forms, such
as figure-of-eight and twisted, giving rise to different manifes-
tations of aromaticity.
In nonpolar solvents (e.g., CH2Cl2), 35 adopts a figure-of-
eight conformation and displays features consistent with those of
a weakly antiaromatic Hückel species, as inferred from spectral
studies and an X-ray crystallographic analysis (Figure 41a,b). In
contrast, in more polar media (e.g., MeCN) or at low
temperature in solvents of intermediate polarity, such as
tetrahydrofuran (THF), topological switching to a Möbius-
twisted geometry occurs, as evidenced from the characteristic
spectral features143 that mirror those seen in Möbius aromatic
[28]hexaphyrins (e.g., emergence of an intense and sharp Soret
band) (Figure 42). Evidence that a charge-separated species was
formed upon photoexcitation came from an EPR study carried
out at 77 K under conditions of photoillumination.
Calculations revealed that both the HOMO and LUMO of the
Hückel form, 35-H, are delocalized over the full hexaphyrin π-
circuit, as would be expected for a 28-π-electron species. In
contrast, the HOMOs (up to HOMO − 6) of the twisted form of
35-M are localized on the TTF unit, with the LUMO mainly
delocalized over the hexaphyrin core. It is thus believed that this
conformer gives rise to more effective PET.
The core-modified TTF-annulated porphyrin 36 and its 26-π-
electron expanded rubyrin analogue 37 have also been
reported.144 Compound 36 exhibits features consistent with
intramolecular CT. The syntheses of 36 and 37 are summarized
in Scheme 23. The preparations of these two products mirror one
another, except that different 1:1 mixtures of precursors were
employed. In contrast to what is true for the figure-of-eight form
of 35 (which contains six fused TTF subunits), expanded
porphyrin 37 contains only two TTF-pyrroles. As a consequence,
it was expected to exist as a planar aromatic system.
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The electronic features of the TTF-annulated macrocycles 36
and 37 could be perturbed by a simple protonation (Figure
43a,b). Protonation of the pyrrolic nitrogen centers also served
to enhance the electron-accepting ability of these macrocycles, an
effect ascribed to the presence of a positively charged core.
Therefore, enhanced intramolecular CT processes were expected
in the case of protonated forms. Detailed theoretical calculations
on both the neutral and protonated forms of 36 and 37 revealed
the HOMOs to be situated on the TTF units (Figure 44a,c,e,g),
whereas the LUMOs are mainly localized on the macrocyclic
core and in part on TTF units (Figure 44b,d,f,h). The
distribution of LUMOs changed substantially in both the cases
upon protonation (Figure 44f,h). Such findings are consistent
with the notion that thermal charge transfer in 36 and 37 would
take place more efficiently in the presence of TFA. This is also
inferred from the lower-energy absorption bands and active EPR
signals at about g = 2 seen under ambient conditions in the case of
the protonated forms H2·362+ and H2·372+ in CH2Cl2.
2.5. ExTTF Porphyrins
Another approach to combining the chemistry of TTF with that
of porphyrins involves the formal insertion of a porphyrin core
between the two 1,3-dithiole rings subunits that make up the
TTF molecule (e.g., exTTFs; compounds 38a−d in Scheme
24).145 These formal electron-rich quinoidal-porphyrin ana-
logues were found to exhibit intriguing redox and photophysical
features. For instance, when subjected to two-electron oxidation,
the initial quinoid-type porphyrin spacers show features
consistent with aromaticity as inferred from spectroscopic
studies and the observation that the initial saddle-shaped
nonaromatic species become planar as befits an aromatic
dicationic porphyrinoid structure.
A particular advantage of these systems is that their inherent
properties could readily be controlled by cation complexation.
Scheme 25 illustrates how this coordination chemistry and
subsequent ligand binding to complex 38d can be used to induce
structural changes that, in turn, modulate the electronic
properties of the system as a whole.
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Scheme 20. Synthetic Schemes Giving Rise to Representative TTF-Porphyrins
When a chloride anion is bound to the Zn(II) center of 38d,
the electron-donor ability of the complex is enhanced. This
results in thermal electron transfer from 38d·Cl− to Li+@C60,
which acts as an electron acceptor. This ET event gives rise to a
stable radical-ion-pair complex under ambient conditions.
Addition of pyridine to this complex promotes electron back-
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transfer, demonstrating the necessity of the Zn−halide
coordination bond for the forward reaction. It also demonstrates
the reversible nature of the system.
Single-crystal X-ray diffraction structures of 38a and 38c
revealed severe saddle-like distortions, with the dithiole rings
being bent out of the plane and toward one another in the neutral
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Figure 31. Crystal structures of (a,b) 26, (c,d) 31-H2, and its Zn2+ complex (e,f) 31-Zn: (a,c,e) top view and (b,d,f) side view. (This figure was redrawn
using data that were originally published in refs 126 and 127.)

Figure 32. UV−vis−NIR spectra of porphyrins 28-H2−31-H2

recorded in dichloromethane. Inset: Region of the CT bands enlarged
by a factor of 15. (Reproduced with permission from ref 127. Copyright
2013 Wiley-VCH Verlag GmbH.)

forms (Figure 45b,d). In contrast, the structure of the two-

electron-oxidized form of 38c (i.e., 38c2+ with triflate as the
counteranion) is planar. These structural changes are consistent
with a system that changes from nonaromatic to aromatic upon
oxidation (Figure 45f). A relatively large two-photon absorption
(TPA) cross-section value was found for 38a2+ (1200 GM),
which is much higher than those typically seen for porphyrins
(<100 GM). This is consistent with the proposed aromatic
character.
It was proposed that the dicationic species 38d2+ could be a
component in a three-component supramolecular ensemble that
would give rise to a long-lived photoinduced charge-separated
state. The other partners in this system were tetraanionic zinc(II)
porphyrin-tetrasulfonates (PZn4−) that would associate through
strong electrostatic interactions to produce a triad of net
stoichiometry PZn4−·(38d2+)2 in benzonitrile.146 The chemical
structures of the components along with the supramolecular
complex are shown in Figure 46. An X-ray crystal structure
analysis revealed a slipped-sandwich type 1:2 supramolecular
ensemble wherein the anionic porphyrin PZn4− is sandwiched by
two separate dicationic species, 38d2+ (Figure 47).
When this supramolecular ensemble is subjected to photo-
excitation, efficient PET from a PZn4− subunit to the triplet
excited state 3[38d2+]* occurs to afford charge-separated triplet
states, as revealed by laser flash photolysis and EPR measure-
2673
Figure 33. Representative MO diagrams for 28-H2 and its Zn2+ complex
28-Zn, supporting the intramolecular ET phenomena in TTF-
porphyrins. (Reproduced with permission from ref 127. Copyright
2013 Wiley-VCH Verlag GmbH.)
ments. It was observed that the decay of the charge-separated
state produced from this three-component system obeyed first-
order kinetics. An extremely long-lived charge-separated state,
with a lifetime of up to 83 ms in benzonitrile at 298 K, was
observed. This long lifetime is thought to reflect the spin-
forbidden nature of the electron back-transfer process, as well as a
small electron-coupling term.
2.6. Other Porphyrin−TTF-Based Donor−Acceptor Systems
2.6.1. Donor−Acceptor Systems Based on Porphyrins
with Peripheral TTF Substituents Connected through
Flexible Organic Spacers. A number of synthetic porphyrin-
based D−A ensembles based on the use of TTF units have been
developed through meso functionalizations (Chart 4). Meso-
TTF functionalization provides an important complement to the
peripherally annulated TTF-porphyrins in which the TTF units
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Table 7. Photophysical Data for the TTF-Annulated Porphyrins and a Reference Compound, Tetraphenylporphyrin (TPP)
compd Soret band λabs (nm) Q-band λabs (nm) ε (M−1 cm−1) at Soret band λfl (nm) Φfl τsc (ps)
TPP 420 512, 546, 590, 648 460000 650, 713 0.11 −
23 420 520, 610 186000 650, 710b − −
25 430 520, 590 625000 680, 740b − −
26 441 483, 538, 605 261000 701, 783b − −
27 440 525, 550 696000 710, 770b − −
28-H2 421 511, 542, 587 467000 647, 713 ≤0.01 4, 112, long
28-Zn 427 547, 575 519000 593, 645 ≤0.01 2, 8, long
29-H2 429 515, 547, 575 381000 − − 2.6, 20
29-Zn 432 547, 575 412000 − − 1.5, 7
30-H2 431 519, 554, 606 332000 − − 1.2, 13
30-Zn 438 547, 577 346000 − − 1.2, 6
31-H2 438 526, 560, 606 283000 − − 1, 10
31-Zn 443 547, 581 297000 − − 1, 5
a
Measurements were performed at 298 K in tetrahydrofuran for compounds 23−27 and in CH2Cl2 for compounds 28−31. bEmission maxima [in
(THF), 298 K] of compounds 23−27 were measured after the addition of FeCl3 as a potential oxidant. cTA measurements were carried out in
toluene at 298 K. For compounds 28−30, the excitation wavelength was 510 nm for the free-base forms and 540 nm for the Zn2+ complexes. For
compound 31-H2, excitation was carried out at 560 nm; for 31-Zn. an excitation wavelength of 580 nm was employed.

acceptor in opposing meso positions.147,148 The synthetic route

Figure 34. Square-wave voltammagrams of selected TTF-porphyrins as
determined in CH2Cl2 containing 0.1 M tetra-n-butylammonium
hexafluorophosphate as the supporting electrolyte: (a) free-base
derivatives 28-H2−31-H2 and (b) their corresponding Zn2+ complexes
28-Zn−31-Zn. (Reproduced with permission from ref 127. Copyright
2013 Wiley-VCH Verlag GmbH.)
share the porphyrin plane (vide supra). This is because meso
substitution can serve to reduce or sever the electronic
interactions between the individual D−A components, which
might be expected to affect, among others, intramolecular
electron-transfer events. In fact, depending on the distance and
orientations of the TTF units connected to the meso positions of
the porphyrins, very different excited-state dynamics, redox
behavior, and nonlinear optical properties might be expected.
In pioneering work, Gust and co-workers synthesized several
molecular systems containing a porphyrin core attached to a
TTF-donor alone (39) or in combination with a C60 (40a,b)
2674
leading to compounds 40a,b is given in Scheme 26. The
combination of substituents appears to have little effect on the
ground-state optical features of the system. For instance, there is
practically no significant interaction between the TTF unit, the
porphyrin core, and the C60 moiety. This was evidenced by an
absorption spectral analysis of these triads, which revealed an
essentially a linear combination of the spectral features of the
various subunits. In the excited state, the fluorescence of the triad
40a is significantly quenched compared to that of 39. This was
ascribed to photoinduced electron transfer (PET) as seen in
many TTF-porphyrinoid combinations. Presumably, the pres-
ence of a fullerene acceptor (present in 40a but not 39)
contributes further to this effect and to the formation of a charge-
separated state.
The putative singlet excited state of porphyrin of 40a was
probed by time-resolved optical methods. These analyses
revealed spectral features consistent with the formation of an
intermediate charge-separated state, TTF-P•+-C60•−, that decays
with a lifetime of 25 ps. The presence of a zinc(II) center in 40b
affects the ultrafast electron transfer from the singlet porphyrin to
the C60 because of its inherent acceptor property. In both 40a
and 40b, further internal electron-transfer processes yield the
final charge-separated state, TTF•+-P-C60•− that decays with a
lifetime on the order of 660 ns in 2-methyl-THF for both
systems. The generation of relatively longer charge-separated
states could reflect a lowest triplet state for the species that is
energetically higher than that of charge-separated species,
TTF•+-P-C60•−.
Charge separation within 40a was further analyzed by time-
resolved electron paramagnetic resonance (TREPR) spectros-
copy.149 In 2-methyl-THF glass (at 10 K) and in a crystalline-
phase matrix, the evolution of the spectrum revealed that the final
charge-separated species, TTF•+-P-C60•−, was formed from the
singlet TTF-P*-C60 through an intermediate charge-separated
state, TTF-P•+-C60•−.
Further insights into the photoinduced electron-transfer
features of TTF porphyrins came from the study of meso-
functionalized, TTF-appended-porphyrins (i.e., 41a,b−44)
characterized by differing substituents and linkage patterns
(Chart 4). Porphyrin 41a and its Zn(II) complex 41b, bearing
TTF subunits attached directly to the meso positions, were
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Table 8. Redox Formal Potentialsa,b,c (V vs Fc/Fc+) of TTF-Annulated Porphyrins

compd Ered2 (V) Ered1 (V) Eox1 (V) Eox2 (V) Eox3 (V) Eox4 (V) Eox5 (V) ref
PnS-TTF-pyrrolea
− − −0.010 +0.445 − − − 126
PrS-TTF-pyrroleb − − +0.284 +0.661 − − − 127
TPPa −2.010 −1.675 − − − − − 126
23 −1.640 −1.340 +0.275 +0.500 − − − 126
24c −1.650 −1.385 +0.040 +0.405 − − − 125
25 −1.810 −1.570 −0.150 −0.020 +0.360 − − 126
26 −1.770 −1.510 +0.030 +0.270 − − − 126
27 −1.660 −1.320 +0.080 +0.150 +0.250 +0.400 +0.510 126
P-H2 −1.481 −1.055 − − − − − 127
P-Zn −1.528 −1.117 − − − − − 127
28-H2 −1.625 −1.257 +0.124 +0.466 − − − 127
28-Zn −1.638 −1.253 +0.178 +0.434 − − − 127
29-H2 −1.538 −1.205 +0.102 +0.318 +0.441 +0.723 − 127
29-Zn −1.692 −1.235 +0.148 +0.468 − − − 127
30-H2 −1.185 −0.963 −0.123 +0.022 +0.164 +0.258 − 127
30-Zn −1.523 −1.229 +0.174 +0.479 − − − 127
31-H2 −1.015 −0.754 +0.452 +0.618 +0.798 − − 127
31-Zn −1.501 −1.189 +0.223 +0.529 − − − 127
a
Measurements for compounds 23, 25, 26, and 27 were carried out at room temperature in THF containing 0.1 M TBAPF6 as the supporting
electrolyte under an Ar atmosphere and using platinum electrodes as the working and counter electrodes. bMeasurements for the remaining
compounds (viz., P-H2, P-Zn, and 28−31) were carried out in CH2Cl2 containing 0.1 M TBAPF6 as the supporting electrolyte under an Ar
atmosphere and using Pt electrodes as the working and counter electrodes. A silver quasireference electrode was used, and the scan rate was 0.02 V
s−1. cMeasurements for compound 24 were carried out in CH2Cl2 under identical conditions to those described footnote a with a scan rate of 0.1 V
s−1.

Figure 35. SEM image showing the spherical aggregation pattern of 32.
(Reproduced with permission from ref 136. Copyright 2010 Royal
Society of Chemistry.)

Figure 36. Chemical structure of the proposed supramolecular complex

reported by Otsubo and co-workers.150 The synthesis of 41a was
achieved by means of a P(OMe)3-mediated cross-coupling of
4,5-bis(methylthio)-1,3-dihiol-2-one and the meso-thioxo-1,3-
dithiol-4-yl-substituted porphyrin (N), as summarized in Scheme
27. The key precursor N could be prepared by three independent
condensation methods as shown in Scheme 27.
There is apparently no interaction between the TTF unit and
the porphyrin moiety in these compounds in their ground state;
presumably, this is due to the orthogonal meso-linking mode. It
was also observed that the emission was quenched by 82% in
toluene, compared to the unsubstituted reference porphyrin,
TPP. As is true for other TTF-porphyrins, this was ascribed to
electron transfer from the TTF subunit to the porphyrin
chromophore upon photoexcitation. Chemical oxidation of the
TTF unit present in 41a by 0.25 equiv of FeCl3 in toluene led to
enhancement of the porphyrin emission by 12% relative to the
TTF-annulated porphyrins. This is presumably due to the fact
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formed by 32 and C60Im.
that oxidation reduces the ability of the TTF subunit to function
as an electron donor. Interestingly, however, further addition of
FeCl3 resulted in the quenching of emission; this was ascribed to
porphyrin oxidation rendering that particular component
ineffective as a photodonor.
Shen and co-workers reported a similar class of TTF−
porphyrin conjugates with flexible alkyl linkers (42−44).151,152
Studies of the absorption spectra revealed prominent features
diagnostic of CT interactions. Upon photoexcitation, the
emission of compounds 42−44 was quenched by 61%, 51%,
and 71%, respectively, compared to the reference TPP; again, this
was ascribed to intramolecular photoinduced electron transfer.
Within this series, the degree of fluorescence quenching is largest
in the case of triad 44, which bears two TTF units trans to one
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Figure 37. MO diagrams for (a,b) 32 and (c,d) its supramolecular
complex 32·C60Im. (Reproduced with permission from ref 136.
Copyright 2015 Royal Society of Chemistry.)
another. Such a finding provides support for the appealing
conclusion that the extent reflects that CT and other related ET
effects are directly proportional to the number and placement of
the TTF units attached to the porphyrin core, at least within this
congruent set of derivatives.
Stoddart and co-workers reported a photoactive supra-
molecular machine based on a TTF−porphyrin−C60 triad, 45.
This triad was proposed as a model compound that could help set
the stage for the use of supramolecular pseudorotaxanes in
energy storage applications (Figure 48).153,154 With this goal in
mine, triad 45, which bears disulfide-based anchoring groups
linked to the terminal TTF unit, was self-assembled on a gold
electrode (giving a coverage value of 1.4 nm2 per molecule).
Generation of a photocurrent under conditions of illumination of
Scheme 21. Synthesis of Quinoxaline-Fused TTF-Porphyrins and Porphyrin Arrays
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Figure 38. UV−vis−NIR spectral changes seen for a 7.16 × 10−6 M
CH2Cl2 solution of 33a upon successive addition of aliquots of
[Fe(bpy)3](PF6)3: (a) 0−1 and (b) 1−2.2 equiv of [Fe(bpy)3](PF6)3.
(Reproduced with permission from ref 138. Copyright 2012 Wiley-
VCH Verlag GmbH & Co.)
the resulting photoelectrochemical cell was inferred based on the
photoaction spectrum of the self-assembled monolayer (SAM)
produced by using 45 in this way. The quantum efficiency of the
system was estimated to be ∼1%, based on the observed
photocurrent output of 1.3 μA cm−2 when the irradiation source
was a 26 mW cm−2 laser operating at 413 nm.
The electrical energy generated by this photoirradiated triad
system was exploited to drive a supramolecular machine for
dethreading of a [2]pseudorotaxane, a 1,5-bis[(2-
hydroxyethoxy)ethoxy]naphthalene (BHEEN) encapsulated
within a tetracationic cyclobis(paraquat-p-phenylene),
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Table 9. Formal Redox Potentials (V vs Fc/Fc+)a of electrons generated during the irradiation [i.e., 3.3 × 10−8 mol/
Quinoxaline-Fused TTF-Porphyrins (4.7 × 10−7 mol) ≈ 7%].
A second-generation redox-/photoactive multicomponent
compound Eox4 (V) Eox3 (V) Eox2 (V) Eox1 (V) Ered1 (V) Ered2 (V)
system was reported by Credi and co-workers.155 This system
33a − +0.85 +0.60 a
+0.15 −1.58 −1.77 marries photoinduced redox machinery with an interlocked
33b − +0.64a +0.48 +0.19 −1.03 −1.76b system (464+) that is based on a [2]rotaxane subunit connected
33cc +1.04 +0.80 +0.50 +0.11 −1.44 −1.77 to a light-harvesting porphyrin donor and a C60 acceptor. This
34a − − +0.75d +0.47a −1.62 −1.79 system contains two donor stations, consisting of a TTF
34b − − +0.56d +0.34a −1.71 −2.06 molecule and a 1,5-dioxynaphthalene (DNP) molecule, built
34c − +0.75a +0.61 +0.44a −1.64 −2.06 into the dumbbell component. This molecular shuttle was thus
a
Two overlapping one-electron redox processes are inferred. expected to afford a light-fueled molecular device because of the
b
Irreversible. cPotentials are reported relative to Ag/AgCl in presence of the electron-accepting CBPQT4+ ring. A CT
CH2Cl2; they can be converted to the Fc/Fc+ scale by subtracting interaction between TTF and the CBPQT4+ ring was seen in
0.51 V from the values referenced to Ag/AgCl. dBroad peak.
the resting state, as inferred from the absorption spectrum. The
stability of this resting state is ascribed to a strong π−π CT
interaction between the CBPQT4+ ring and the electron-rich
TTF unit that serves to enforce a thermodynamic advantage for
the TTF portion of the dumbbell residing near the electron-
deficient CBPQT4+ ring. Upon oxidation of the TTF unit,
electrostatic repulsion between the CBPQT4+ ring and the
charged TTF•+ radical ion shifts the thermodynamics of the
system such that binding to the second electron-donating site
(the DNP “station”) is favored. Thus, photoinduced nanoscale
molecular motions are induced within the [2]rotaxane consisting
of 464+ and the CBPQT4+ ring (Figure 49). Irreversible oxidation
processes ascribed to the TTF units, appearing at ca. +0.51 and
+0.91 V (vs SCE) were observed. These could reflect the
complicated conformational flexibility (e.g., folding), which
induces a partial displacement of the CBPQT4+ ring away from
Figure 39. Schematic representation of the supramolecular triad 33b· the TTF station in 464+.
C60Py formed through the axial coordination of C60Py to 33b and its Movement of the CBPQT4+ ring along the linear portion of
proposed intermolecular charge-transfer pathway. 464+ could also be achieved by reduction of the bipyridinium
moiety at a potential of −0.28 V. The resulting destabilization of
the CT interactions with either the TTF or DNP donor units
facilitates free movement along the thread as inferred from
spectroelectrochemical measurements.
In a strategy that bears some analogy to the alkyne-bridged
porphyrin dimers156−158 and TTF-annulated dumbbell porphyr-
in dimers, 34a−c,137,138 discussed earlier, an A−π−D−π−A-type
TTF-porphyrin dimer, 47, was reported by Ogawa and
Nagatsuka.159 In this system, two porphyrins are bridged by a
diacetylene-TTF unit to give dimer 47. Construct 47 exhibits
features consistent with the presence of effective π-extension, as
evidenced by the large two-photon absorption cross sections
determined by steady-state and time-resolved spectroscopies
(nanosecond open-aperture Z-scan method). The remarkably
large two-photon absorption cross-section values of σ2 = 5900
GM at 760 nm in toluene and 7300 GM in benzonitrile for 47 are
consistent with effective CT and ET within the system. These
Figure 40. Fluorescence spectral changes seen upon the addition of
increasing quantities of C60Py to a solution of 33b in o-dichlorobenzene. values are comparable to those seen for a bisporphyrin directly
(λex = 420 nm.) Inset: Benesi−Hildebrand plot. (Reproduced with connected by a butadiyne bond (σ2 = 7700 GM at 860 nm).160
permission from ref 138. Copyright 2012 Wiley-VCH Verlag GmbH & It was also anticipated that oxidation of the push−pull type of
Co.) TTF-annulated porphyrin species would enhance the static first
hyperpolarizabilities as determined by DFT calculations.161
2.6.2. Donor−Acceptor Systems Consisting of Por-
BHEEN⊂CBPQT4+ (see Figure 48). The electrochemical phyrins with Axially Coordinated TTF Derivatives. Metal-
reduction of cyclobis(paraquat-p-phenylene) (CBPQT4+) weak- loporphyrins are venerable systems that have long attracted
ens the CT interactions, resulting in decomplexation of the attention for use in the construction of efficient CT complexes.
[2]pseudorotaxane, BHEEN⊂CBPQT4+. The reaction could be One approach that has been pursued in the context of this
monitored by measuring the fluorescence intensity of the paradigm involves the preparation of supramolecular D−A
BHEEN moiety at a potential of 0 V. Using this indicator, the multicomponent models that rely on axial coordination to
6.7% increase of the intensity with respected to the initial various porphyrin metal centers. By ligating a TTF donor unit or
intensity was considered to be consistent with the molar ratio of an electron acceptor to a metalloporphyrin, it might be possible
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Scheme 22. Synthetic Route to Expanded TTF-Porphyrin 35 and Its Switching between Limiting Hückel Figure-of-Eight (35-H)
and Möbius-Twisted (35-M) Conformers
Figure 41. Single-crystal X-ray structure of 35: (a) top and (b) side
views. The thermal ellipsoids are scaled to the 50% probability level.
(This figure was redrawn using data that were originally published in ref
139.)
to maximize the spatial separation between charges generated by
photoinduced intracomplex electron transfer. A further
attraction of this approach is that modifications based on
changes in the entities coordinated to the metal centers should be
facile. In fact, a number of groups have reported supramolecular
diads and triads (48−54) based on the use axially coordinated
TTFs as well as, in certain cases, various ancillary electron-
acceptor groups (Chart 5).
One example of a dyad that falls within this general paradigm is
compound 48 reported by Zhu and co-workers.162 This system
consists of a pentacoordinated zinc(II)porphyrin bearing a
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Review
Figure 42. UV−vis−NIR absorption spectra of 35 recorded in various
mixtures of CH2Cl2 and MeCN. (Reproduced with permission from ref
139. Copyright 2013 Royal Society of Chemistry.)
pyridyl-substituted TTF derivative ligated to the metal center
(Chart 5).
The coordination of the TTF unit to ZnP was analyzed by
means of a UV−vis absorption spectral titration. Analysis of the
resulting profile revealed a 1:1 binding constant of 4.71 × 104
M−1. Upon binding of the TTF unit (to produce 48), the
fluorescence intensity of the porphyrin subunit was quenched
relative to that of the starting porphyrin (ZnP). This quenching is
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Scheme 23. Synthetic Routes to 36 and 37 and Schematic Representations of Their Protonated Forms
Figure 43. UV−vis−NIR absorption spectra of (a) compounds 36
(black) and H2·362+ (red) and (b) compounds 37 (black) and H2·372+
(red) as measured in CH2Cl2. Insets: Magnified NIR region and
photographs of solutions of the neutral and diprotonated forms of
compounds (a) 36 and (b) 37 under ambient light. (Reproduced with
permission from ref 144. Copyright 2015 Royal Society of Chemistry.)
ascribed to an electron-transfer process, in which the ZnP
macrocycle acts as an electron acceptor and the overall transfer is
favored by a driving force of −0.33 eV. However, the degree of
quenching for the coordinated complex 48 was less than that
seen for typical TTF-annulated porphyrins (e.g., 23 and 24), a
result that likely reflects the inherently large separation between
the TTF subunits and the ZnP site of complexation.
Lateral π-extended supramolecular triads (e.g., 49 and 50)
constructed through the coordination of a pyridyl-substituted
TTF unit to the zinc(II) centers of cationic Zn(II)−Au(III)
porphyrin pseudodimers were reported by Odobel and co-
workers.163 The two porphyrins in these pseudodimers were
bridged by either oligophenylene ethynylene (ZnP-OPE-AuP+)
or bisethynyl quaterthiophene (ZnP-quater-AuP+) spacers. As
prepared, these linked porphyrins displayed rapid photoinduced
electron transfer from the ZnP to the AuP+ unit upon
photoexcitation. The resulting charge-separated systems dis-
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played lifetimes of 2.2 and 3.1 ns, respectively.164,165 Upon
complexation of a pyridyl-TTF unit to the zinc(II) center in 49
and 50 (binding constants of Ka = 1.0 × 104 and 1.6 × 104 M−1,
respectively), a hole shift from the oxidized form of ZnP to the
TTF entity occurred following photoexcitation (a driving force
of 0.58 eV was calculated for these systems). Fast electron
transfer from the singlet excited ZnP to the AuP+ moiety
occurred within 70 and 80 ps, respectively, as determined by
transient absorption spectroscopy. Hole shift then occurred to
give the final charge-separated state TTF•+-ZnP-spacer-AuP•−.
The lifetimes of the charge-separated states, 30 and 100 ns for 36
and 37, respectively, were enhanced by 10−50-fold compared to
those of the dyads discussed above (Figure 50a). The
photophysical phenomena associated with this compound are
summarized in Figure 50b.
van der Est and co-workers demonstrated a supramolecular
hole-transfer process in a hypervalent methyl phosphorus(V)
octaethylporphyrin bearing an axially coordinated TTF unit (51)
upon photoexcitation. 1 6 6 In this dyad complex, a
organophosphorus(V) porphyrin was used with the thought
that the high oxidation state of the phosphorus center would
facilitate reduction and help achieve efficient hole transfer
(Scheme 28).
Coordination of a TTF subunit to the phosphorus center (to
afford 51) led to significant fluorescence quenching, which was
ascribed to hole transfer from the excited phosphorus porphyrin
to the TTF subunit (Figure 51a). Evidence for the formation of a
radical pair under these conditions came from time-resolved EPR
(TREPR) spectroscopic analyses (Figure 51b). The observation
of a narrow spectrum with a width of 50 G is consistent with a
triplet state consisting of a moderately strongly coupled radical
pair. Fitting of the decay profiles of the EPR signal allowed a
charge-separated lifetime of ∼300 ns to be calculated.
van der Est and co-workers reported several six-coordinated
D−porphyrin−A supramolecular ensembles based on
aluminum(III) porphyrins.167,168 Aluminum(III) porphyrins
(AlPs) are attractive because they can accommodate two
different axially tethered redox-active partners. For instance,
carboxylic acid derivatives can be used to replace the reactive axial
hydroxide groups typically found in native AlPs, whereas some
bases, such as pyridines, can coordinate to the opposite face of
the AlP framework. This can provide facile access to polarized
supramolecular complexes bearing D and A units that are
vertically arranged relative to the AlP plane (Chart 5).
Two triads (52a and 52b), consisting of an AlP unit with an
axially bound naphthalenediimide carboxylate (NDI) electron-
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Figure 44. (a,c,e,g) HOMO and (b,d,f,h) LUMO diagrams for (a,b) 36, (c,d) 37, (e,f) H2·362+, and (g,h) H2·372+. (Reproduced with permission from
ref 144. Copyright 2015 Royal Society of Chemistry.)
Scheme 24. Synthetic Route to an ExTTF-Porphyrin and Its
Metal Complexes
acceptor unit and a pyridyl-TTF donor unit, were constructed in
this way.167 The binding constant of the axially coordinated
pyridyl-TTF molecule was estimated to be 1.1 × 103 M−1 for a
1:1 receptor/substrate stoichiometry in CH2Cl2. Based on
electrochemical studies, photoinduced electron transfer from
an excited AlP* singlet state to the NDI, hole stabilization on the
TTF unit, and an electron shift to NDI were expected to be
exothermic.
Experimental evidence was put forward to support the
contention that the excited state of the AlP (i.e., singlet AlP*)
is quenched through electron transfer to the NDI moiety and
hole transfer to TTF, giving rise to a TTF•+-AlP-NDI•− radical
pair. Spin-polarized transient EPR spectroscopy carried out in
the nematic phase of a liquid-crystalline solvent (Figure 52a,b),
4-(n-pentyl)-4′-cyanobiphenyl, revealed polarization patterns
consistent with charge separation occurring through singlet−
triplet mixing. The lifetime of the resulting TTF•+-AlP-NDI•−
charge-separated state was estimated to be 200−350 ns
(depending on the choice of spacer) (Figure 52c).168 In contrast,
in an isotropic solvent, such as CH2Cl2 or benzonitrile, the
lifetime was found to be considerably shorter (<10 ns).
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Scheme 25. Schematic Representation of How Cation
Complexation and Ligand Binding Can Be Used to Control
the Electronic Properties of MTTFP and Its Thermal ET to
Li+@C60
van der Est and co-workers reported a series of vertical, linear
supramolecular triads constructed from AlP, TTF-(Ph)n-Py, and
(Ph)m-C60 moieties (compounds 53a−f in Chart 5), where Py
stands for pyridine; Ph stands for phenyl; n = 0, 1; and m = 1, 2,
3.169 The formation of these supramolecular triads was
confirmed by spectroscopic titrations, with Benesi−Hildebrand
plot analyses being used to estimate formation constants in the
range of (1.0−1.5) × 103 M−1. Upon addition of TTF-(Ph)n-Py
(n = 0, 1) to the dyad [AlP-(Ph)m-C60, m = 1−3], supramolecular
triads formed, as evidenced by a decrease in fluorescence
intensity. This decrease is consistent with electron transfer from
TTF to 1AlPor*, a change in the intrinsic fluorescence rates, or
some combination thereof (Figure 53a).
In compounds 53a−f, the acceptor unit is a fullerene (C60),
which is known to have a low reorganization energy. In triads of
the general structure 53, excitation of the AlP subunit leads to
stepwise, sequential electron transfer between the TTF unit and
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Figure 45. Crystal structures of (a,b) 38a, (c,d) 38c, and (e,f) 38c·2CF3SO3−: (a,c,e) front view and (b,d,f) side view. (Reproduced with permission
from ref 145. Copyright 2013 American Chemical Society.)
Figure 46. Chemical structures of the components used to create a
supramolecular triad and a representation of the resulting ensemble.146
the C60 moiety. This gives rise to a charge-separated radical pair
with a relatively long lifetime (i.e., ∼140 ns).169 The time-
resolved EPR spectrum of 53 shows the narrow absorption and
emission band pattern, which is typical of a moderately coupled
radical pair with predominant population in the T0 level at early
times (Figure 53b). At later times, the polarization patterns
become weaker and invert as a result of spin-selective
recombination from states with singlet character. The weak
distance dependence between the TTF unit and C60 in the
electron back-transfer was considered indicative of a super-
exchange mechanism.
Modulation of the excited-state dynamics could be achieved by
replacing the fullerene acceptor by the electron-deficient free-
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Figure 47. X-ray crystal structure of the supramolecular complex with a
net stoichiometry of PZn4−·(38d2+)2. (This figure was redrawn using
data that were originally published in ref 146.)
base and cationic gold(III) porphyrin acceptors to give triads 54a
and 54b, respectively (Chart 5). In the case of the free-base triad
54a,170 the energy- and electron-transfer characteristics of the
AlP core could be tuned by changing the solvent polarity or by
adding a TTF donor unit. Specifically, it was found that, In
CH2Cl2 or o-dichlorobenzene, singlet energy transfer occurs
from the excited AlP* singlet state to the free-base porphyrin
acceptor with a rate constant, kEnT, of 1.78 × 108 s−1 in the
absence of an added TTF unit. Upon complexation of the TTF
donor, ultrafast electron transfer from TTF to AlP* occurs
following photoexcitation with rate constants, kET, of (8.33 ×
109)−(1.25 × 1010) s−1, depending on the specific system in
question. A subsequent electron shift to the free-base porphyrin
then occurs to generate the radical ion pair TTF•+-AlP•−-H2P.
This species subsequently undergoes an intraensemble electron
transfer to generate a spatially well-separated TTF•+-AlP-H2P•−
radical pair (Figure 54). Time-resolved EPR spectroscopy
revealed that this latter radical pair is formed through the triplet
state of the free-base porphyrin and that the exchange coupling of
the two spins in 54a is ferromagnetic.171
In the case of the triad 54b (cf. Chart 5), having a cationic
gold(III) porphyrin (AuP+) as the electron acceptor, spectral
overlap between the emission and AuP+ absorption is
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Chart 4. Chemical Structures of Compounds 39−47 Containing Porphyrins Bearing Meso TTF Substituents
observed.172 This facilitates quenching of the fluorescence
through intraensemble electron transfer. Because of the greater
electron-accepting ability of a AuP+ porphyrin complex relative
to the corresponding free base, the lowest excited singlet state of
AlP* was quenched by ultrafast electron transfer to AuP+ with
halflives of 18.5−61.2 ps, depending on the specific choice of
spacers that serve to link the components. As in the
corresponding free-base system discussed above, intracomplex
ET processes ultimately give rise to a charge-separated radical
pair. The lifetime of the charge-separated state was estimated to
be 1.4−1.5 ns, with the specific value depending on the number
of phenylene spacers in the compound subject to study (i.e.,
choice of donor in 54b).
2.6.3. Supramolecular Nonbonded Donor−Acceptor
Ensembles of Porphyrin and TTFs. A variety of supra-
molecular D−A architectures constructed from TTF subunits
and porphyrins through nonbonding interactions, such as
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hydrogen-bonding and electrostatic interactions, are now
known. For instance, Fukuzumi and co-workers reported a
highly distorted saddle-shaped diprotonated porphyrin, O
(Figure 55a−c), that forms D−A-type supramolecular ensembles
through π−π donor−acceptor interactions with a suitable
electron-rich guest molecules, such as TTF (Figure 56a).173
Whereas many coplanar porphyrins have been used as electron
donors, this highly strained porphyrin (a consequence of the
dodecaphenyl substituents) can act as an electron acceptor,
making it attractive for the construction of supramolecular D−A
charge-transfer systems.
A single-crystal X-ray diffraction analysis of the complex
formed between TTF and the dication O revealed that the TTF
is encapsulated within the inner cavity created by the peripheral
phenyl groups on the porphyrin. This results in the formation of
TTF-entrapped supramolecular porphyrinic nanochannels
(PNCs) (cf. Figure 56b).
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Scheme 26. Synthesis of Compounds 40a,b
Scheme 27. Synthetic Route Leading to the Meso-Linked Porphyrins 41a,b
The photoconductivity of a single crystal of TTF-PNC was
studied. A photocurrent of 0.7 nA was recorded at an electrical
field strength of 3.5 × 104 V cm−1. The photocurrent was found
to be dependent on the axis, providing support for the conclusion
that the intermolecular π−π stacked arrangement shown in
Figure 56b is correlated with the greatest conduction pathway.
The supramolecular TTF-PNC complex was also used to
construct photoelectrochemical cells (Figure 57a). A photo-
induced current was generated and the maximum incident-
photon-to-current efficiency (IPCE) performance of the cell was
determined to be 10.1% at 460 nm when an OTE/SnO2/PCN-
TTF anode was employed (Figure 57b), where OTE represents
optically transparent electrode [e.g., F-doped tin oxide (FTO)].
The excited-state dynamics of hydrogen-bonded supra-
molecular PET processes were also probed174 using a
combination of TTF carboxylate derivatives as the electron-
donating guests (along with other putative donor molecules) in
conjunction with the diprotonated dodecaphenylporphyrin (O).
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The formation of a 1:2 hydrogen-bonded supramolecular
complex (with a formation constant, K, of 1.9 × 1010 M−2) was
confirmed by spectroscopic measurements. From time-resolved
measurements, an intrasupramolecular PET reaction from the
hydrogen-bonded TTF-carboxylate to the porphyrin O was
inferred. This gave a charge-separated species at room temper-
ature. The rate constants corresponding to forward electron
transfer (kET) and backward electron transfer (kBET) were
determined to be 7.4 × 1011 and 1.8 × 1011 s−1, respectively, in
benzonitrile at room temperature.
The supramolecular electron-transfer behavior of the TTF-
bridged bis(β-cyclodextrin) derivative (TTFCD) was inves-
tigated by Liu and co-workers in the absence and presence of
porphyrins.175 Cyclodextrins (CDs), cyclic oligosaccharides
linked by α-1,4-glucose bonds, have been used to complex a
large number of guests within their central cavities.176
Combining a TTF-bridged CD dimer with a porphyrin (P)
was found to give rise to a unique noncovalent D−A
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Figure 48. Schematic representation illustrating how the light-driven
power supply (i.e., the triad 45) provides the electrical energy needed to
dethread a [2]pseudorotaxane ([2]PR) wherein BHEEN is encapsu-
lated inside the cavity of the CBPQT4+ cyclophane. The curved arrows
show the vectorial electron transfer from the photoexcited porphyrin
chromophore to the C60 component. This transfer is followed by a
charge shift to the TTF component. Charge neutralization by the Au
electrode then results in a closed circuit. Electron transfer to the
pseudorotaxane leads to dethreading of the reduced CBPQT•/3+ before
the electron is passed on to the Pt counter electrode. (This figure was
redrawn using data that were originally published in ref 154.)
nanoarchitecture in aqueous media. The basic recognition
chemistry is shown schematically in Figure 58.
A quenching of the porphyrin fluorescence was observed when
the water-soluble meso-tetrakis(4-sulfonatephenyl)porphyrin
(P) was allowed to interaction with the TTF-bridged bis(β-
Figure 49. Schematic representation of a bistable mechanical switch composed of 46 (in different charge states), CBPQT4+, DNP, and TTF•+.
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CD) host under buffered aqueous condition. The binding
constant was estimated to be Ka = 3.50 × 105 M−1 with the
underlying data fitting well to a 1:1 binding profile. This is
consistent with formation of a linear supramolecular assembly.
The porphyrin fluorescence was recovered upon treatment of the
ensemble with H2O2 or oxidation by electrochemical means.
This finding provides support for the proposal that the excited
porphyrin is quenched by intraensemble PET (cf. Figure 58).
A similar type of supramolecular nonbonded complex, namely,
ionic CT dyads formed between a cationic porphyrin and an
anionic TTF derivative, was reported by Dai and co-workers.177
In this case, simple mixing of a N-methylated tetrakis(4-
pyridyl)porphyrin (TMPyP) cation and the TTF-bicarboxylate
(L1) or tetracarboxylate (L2) derivatives afforded the ion-pair
complexes TMPyP/L1 and TMPyP/L2 (Figure 59a,b).
Complexes TMPyP/L1 and TMPyP/L2 were characterized
by broad absorption features in the 750−1200 nm spectral region
that were attributed to anion−cation charge-transfer transitions.
Clearly discernible chemical shifts for the β-pyrrolic protons in
the 1H NMR spectrum, along with an EPR signal at g ≈ 2 and
fluorescent quenching in solution, were seen. This was taken as
evidence of complete or partial CT occurring within these
complexes.
A photoelectrochecmical cell was prepared using TMPyP and
L1/L2. A photocurrent response was observed under conditions
of photoillumination (Figure 60). This result, which parallels
those discussed above, was rationalized in terms of an effective
photoinduced electron-transfer process.
2.7. TTF-Functionalized Porphyrazines
2.7.1. TTF-Annulated Unsymmetrical and Symmetrical
Porphyrazines. Porphyrazines (Pzs), or tetraazaporphyrins, are
analogues of porphyrins, wherein the meso carbon atoms are
replaced by nitrogen atoms.178,179 Porphyrazines have attracted
attention as potential optoelectronic materials because of their
desirable photophysical properties, including intense π → π*
transitions in the visible region. When TTFs are annulated or
otherwise synthetically appended to these macrocyclic systems,
interesting hybrid molecular motifs are generated that, in many
instances, display unique optical and magnetic properties.
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Chart 5. Chemical Structures of Some Supramolecular Di- and Triads Containing Porphyrins with Axially Coordinated TTF
Derivatives
Figure 50. (a) Nanosecond transient absorption spectra and best fits for
the bleaching of the AuP Soret band at 418 nm for dyad 49 in
dichloromethane (red); dyad 50 in toluene (blue); and for reference, a
quaterthiophene dyad without a secondary donor (black). All traces
were obtained after excitation of the Q-band of the ZnP moiety. The
solutions were deaerated by bubbling with Ar. (b) Summary of the
photophysical processes occurring in the triads produced by complex-
ation of a TTF subunit. (Reproduced with permission from ref 163.
Copyright 2010 Royal Society of Chemistry.)
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Yin and co-workers reported a series of symmetrical180−182
and unsymmetrical183 TTF-annulated metalloporphyrazines
with various peripheral substitutuents (structures 55−57 in
Chart 6). These compounds were prepared through the
cyclotetramerization of appropriately chosen dicyano-TTF
derivatives. Their optical, electrochemical, and aggregation
properties were then analyzed.
The syntheses of representative unsymmetrical and sym-
metrical porphyrazines are summarized in Scheme 29. The key
preparative step involves the Mg(II)-templated macrocyclization
of a 2,3-dicyano-TTF precursor (e.g., DCTTF1 to synthesize
55b) in an alcoholic solvent at reflux.
The 1H NMR spectra of 56a−c recorded in CDCl3 revealed
broad signals. This broadening was thought to reflect the
presence of a radical contaminant, such as TTF•+, or slow
molecular tumbling on the NMR time scale due to aggregation of
the compound. Broadening of both the Soret and Q-bands was
also noted in the UV−vis spectra; this was attributed to n → π*
electronic transitions involving nonbonding electrons associated
with the peripheral S and N atoms, as well as strong aggregation
resulting from Pz−Pz, Pz−TTF, and TTF−TTF π−π
interactions. Dynamic light scattering (DLS) measurements
provided support for the conclusion that the monomeric forms of
these compounds self-assemble in solution to form near-uniform
aggregates that are approximately 200 nm in size. Further
evidence for aggregation came from transmission electron
microscopy (TEM) experiments.
Incorporation of electron-withdrawing ester groups at the
periphery of the TTF units served to reduce the donor properties
of these compounds. This meant that effective ET was seen only
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Scheme 28. Synthesis of Compound 51
Figure 51. (a) Emission spectra of 51, its oxidized form 51•+, and the
reference POEP-OMe (λex = 418 nm). (b) Time-resolved EPR spectra
of the reference compound POEP-OMe and 51, recorded at 5 °C in a
liquid-crystalline matrix consisting of 4-pentyl-4′-cyanobiphenyl (5CB).
(This figure was redrawn from data originally published in ref 166.)
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in the case of strong acceptors. For example, when compound
57c was mixed with TCNQ, no CT band was observed in the
600−1000-nm spectral region. However, when a stronger
electron-withdrawing acceptor, namely, 2,3,5,6-tetrafluoro-
7,7,8,8-tetracyanoquinodimethane (F4TCNQ), was used in
conjunction with 57c, CT transitions were observed at 756
and 863 nm (Figure 61a). The formation of a 57c•+/F4TCNQ•−
radical ion pair was confirmed by EPR spectroscopy (Figure
61b).
Electrochemical analyses of compounds 56 and 57 in a
CH2Cl2/MeCN mixture revealed one reduction signal for each
compound. These redox events were ascribed to porphyrazine-
centered processes. In contrast, multiple signals were observed in
the oxidative region, a finding considered to reflect redox events
involving the various subunits present in the overall framework.
Su and co-workers carried out an in-depth theoretical
calculation184 on a simplified form of the TTF-annulated
Zn(II)-porphyrazine ZnTTFPz (56c). This model system was
identical to 56c but lacked the peripheral butyl substituents (so
as to reduce the required computation time). Also examined
were two controls, namely, an unsubstituted normal Zn(II)-
porphyrazine and Zn(II)-TPP. A goal of this study was to
understand the origin of the unusually broad, intense, and red-
shifted Q-band.
The vertical excitation energies of the compounds were
calculated using time-dependent density functional theory
(TDDFT) and compared to the experimental UV−vis
absorption spectra. On this basis, it was concluded that the Q-
band of ZnTTFPz is dominated by a TTF → Pz charge-transfer
transition that mixes with those arising from the porphyrazine
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Figure 52. Room-temperature (300 K) transient EPR spectra of
compound 52 recorded in the nematic phase of a liquid crystal, 4-(n-
pentyl)-4′-cyanobiphenyl. (a) Wide scan showing a broad, very weak
contribution from 3AlP and intense narrow peaks from TTF•+-AlP-
NDI•− 300 ns after the laser flash. (b) Features ascribed to TTF•+-AlP-
NDI•− viewed using an expanded scale: solid line, 300 ns after the laser
flash; dashed line, 1.1 μs after the laser flash. The arrow under the spectra
indicates the field position used to record the spectroscopic transients
used for the lifetime analyses. (c) Signal decay associated with the
proposed charge recombination that occurs in complex 52 following
photoirradiation. (Reproduced with permission from ref 167. Copyright
2013 Wiley-VCH Verlag GmbH.)
core. The Q-band of ZnTTFPz was found to mix with other
configurations, meaning that the system could not be analyzed in
terms of Gouterman’s classic four-orbital model that has been
used so successfully for the spectral interpretation of many
tetrapyrrolic systems. On the other hand, the match with
experiment (maximum error in the excitation energies of 0.17
eV) provided support for the notion that TDDFT/statistical
average of orbital potentials (SAOP) performs well in predicting
the Q- and B-bands, at least of ZnTTFPz.
2.7.2. Porphyrazines Peripherally Modified with TTFs
through Saturated Spacers. TTF-Thia-Crown-Ether-Func-
tionalized Porphyrazine. Yin and co-workers also reported a
TTF-thiacrown-ether-annulated porphyrazine185 (58). This
compound was obtained using the same basic Mg2+-templated
macrocyclization process as described above; in this case,
precursor Q was employed (cf. Scheme 30).
The porphyrazine system 58 was investigated by electro-
chemical methods and CT studies. As is true for other
porphyrazines described earlier in this review, no evidence of
electron transfer from 58 to TCNQ was seen, even when the
latter putative acceptor was present in excess. However, when
F4TCNQ was used, an intermolecular CT complex, assigned to
the 58•+/F4TCNQ•− radical ion pair, formed, as inferred from
the appearance of two CT bands (λmax = 759 and 863 nm) in the
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Figure 53. (a) Fluorescence titrations of AlP-(Ph)2-C60 with TTF-Py in
o-dichlorobenzene. Excitation (λex) was effected at a wavelength
corresponding to the isosbestic point, 555 nm, as determined by
independent UV−vis titrations. (b) Room-temperature spin-polarized
transient EPR spectra of TTF-(Ph)n-Py-AlP-(Ph)m-C60 triad. The
spectra on the right and left have been extracted from the time and field
data sets associated with the 75- and 550-ns time windows, respectively.
The black traces are experimental spectra, and the red traces are
simulations. (Reproduced with permission from ref 169. Copyright
2016 Royal Society of Chemistry.)
steady-state absorption spectrum (Figure 62a). These two newly
generated bands correspond to the SOMO → LUMO electronic
transition that produces 58•+. Support for this conclusion came
from EPR spectroscopic studies (Figure 62b). Specifically, peaks
at g = 2.0078 and g = 2.00176 are seen in the EPR spectrum
recorded at room temperature in CH2Cl2 that are ascribed to the
TTF radical cation (TTF•+)186,187 and the F4TCNQ radical
anion (F4TCNQ•−)188,189 generated as the result of the
proposed CT process.
Broadening of the Q-band as well as the B-band was seen in the
case of 58. This broadening was thought to be due to n → π*
electronic transitions involving the nonbonding electrons of the
peripheral S and N atoms. An electrochemical analysis of 58
revealed two one-electron reduction processes at −1.177 and
−0.937 V that are associated with reduction of the magnesium-
(II)-porphyrazine core (Table 10). In addition, three signals
were seen in the oxidative region. These are ascribed to multiple
oxidation processes and are thought to reflect interactions
between two neighboring TTF units, which allow species such as
TTF•+, [(TTF)2] •+, and TTF2+ to be stabilized.
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Figure 54. Proposed energy-/electron-transfer pathway operative in
dyad (AlP-H2P) and triad 54a.
Figure 55. (a) Chemical structure of O. (b,c) Single-crystal X-ray crystal
structure of O: (b) top view and (c) side view showing the saddle-like
distortion from planarity. (This figure was redrawn using data that were
originally published in ref 173.)
Porphyrazine Peripherally Attached to TTFs through
Saturated Thia-Ether Bridges. Yin and co-workers reported190
a metalloporphyrazine, 59, wherein eight peripheral TTF units
are connected to the macrocyclic core through saturated thia-
ether linkages at all of the β-positions of pyrroles. Compound 59
was synthesized by the magnesium propoxide-promoted cyclo-
tetramerization of precursor R in propanol at reflux, as shown in
Scheme 31.
The UV−vis spectrum of 59, recorded in a mixture of CHCl3
and MeCN, was characterized by a broad Q-band centered at 678
nm (ε = 58000 M−1 cm−1), as well as a Soret-like transition that
was thought to reflect transitions involving both the Mg(II)-Pz
ring and the TTF substituents. Broadening of both the Q- and B-
bands was attributed to n → π* transitions involving the
nonbonding electrons of the peripheral S and N atoms that
overlap with the pure Mg(II)-Pz ring-derived bands. To
investigate the ability of compound 59 to act as an electron
donor, a doping experiment was carried out in a mixture of
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CHCl3 and MeCN (3:1, v/v) using an excess of TCNQ. Under
these conditions, two new absorption bands at 747 and 847 nm
were observed, in analogy to what was found for 57c (Figure 61a)
and 58 (Figure 62a). These new bands were assigned to
SOMO−LUMO transitions of the TTF cation radical species
present in the radical ion pair produced under these conditions,
namely, 59•+/TCNQ•−.
Electrochemical investigations revealed a total of four redox
waves. One, at −0.693 V vs SCE, was assigned to Pz-core
reduction (i.e., Pz2−/Pz3−). The other three, at +0.563, +0.938,
and +1.218 V vs SCE, were assigned to TTF•+/TTF, TTF+2/
TTF•+, and Pz−/Pz2− oxidative processes, respectively.
2.7.3. Pyrazinoporphyrazine with Peripheral TTF Units
Tethered by Flexible Spacers. A unique type of pyrazino-
porphyrazine derivative (60a−c) containing eight TTF units
attached at the periphery of the macrocyclic core was reported by
Howard and co-workers.191 This compound was synthesized by
subjecting a TTF-tethered 2,3-dicyanopyrazine-based precursor,
S, to cyclotrimerization (Scheme 32).
The main precursor, S, was obtained in a straightforward
manner using procedures analogous to those used to prepare
other unsymmetrical TTF derivatives. It was then subjected to
lithium pentoxide-promoted macrocyclization at high temper-
ature. The 1H NMR spectra of 60a−c, recorded in a wide range
of solvents at 20 °C, were characterized by broad signals. The
UV−vis absorption spectra of 60b,c in CH2Cl2 showed a single
Q-band-like absorption feature centered at λmax values of 659 and
664 nm in the cases of 60b and 60c, respectively. Upon addition
of excess iodine to a CH2Cl2 solution of 60b, a new broad low-
energy absorption band emerged beyond 800 nm, a finding that
was interpreted in terms of the formation of TTF•+. The
nonemissive nature of these compounds was explained in terms
of intramolecular CT between the TTF units and the excited
state of the pyrazinoporphyrazine core, in analogy to other TTF-
annulated macrocyclic systems discussed in this review (vide
supra).
Electrochemical analysis of 60a−c in a range of pure and mixed
solvents provided support for the notion that the adjacent TTF
units present at the periphery of the macrocyclic core do not
interact with each other. As a consequence, two clear sets of
oxidation waves are seen that are similar to those of the precursor
S. The reversibility of the oxidation procedure decreases as the
solubility of the compound in question (i.e., 60a > 60b > 60c)
decreases.
2.8. TTF-Functionalized Phthalocyanines
2.8.1. TTF-Annulated Symmetrical Phthalocyanines.
Phthalocyanines192−194 (Pcs) are venerable pigments that, like
porphyrazines, are structurally related to the porphyrins. The
parent Pc framework contains four isoindole subunits linked by
four meso nitrogen atoms. Pcs can be viewed as 18 π-electron
aromatic systems that act as planar dianionic N4 macrocyclic
ligands for a variety of metal cations. In fact, most Pcs are far
more stable in their metalated forms. The meso nitrogen atoms
alter the MO interactions relative to what is typical for
porphyrins, especially in terms of destabilizing the HOMOs.
One consequence of this modulation is intense Q-band(s) for
Pcs that are observed at about 700 nm in the visible region. This
transition has made Pcs attractive for their photophysical
properties and made them widely used as functional dyes and
industrial pigments. From an electrochemical perspective, Pcs
behave as the electron acceptors, particularly when they are
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Figure 56. (a) Schematic diagram of the supramolecular D−A ensemble that results from treating the diprotonated saddle-shaped porphyrin host O
with the electron donor TTF. (b) Crystal packing diagram of the ensemble illustrating the columnar structure that persists along the crystallographic c
axis. Solvent molecules have been omitted for clarity. (This figure was redrawn using data that were originally published in ref 173.)

Figure 57. (a) Sample arrangements used in photoconductivity

measurements of a single crystal of PNC-TTF. (b) Schematic
description of a photoelectrochemical cell employing an OTE/SnO2/
PNC-TTF anode. (Reproduced with permission from ref 173.
Figure 59. Schematic representation of two different supramolecular
Copyright 2008 American Chemical Society.)
structures formed when cationic TMPyP is exposed to anionic TTF
carboxylates (L1 and L2). (This figure was redrawn using data that were
combined with TTF electron donors. This has made Pcs originally published in ref 177.)
functionalized with TTF subunits desirable synthetic targets.

Figure 58. Schematic representation of the supramolecular ensembles formed from TTFCD and porphyrin P in aqueous media. (This figure was
redrawn using data that were originally published in ref 175.)

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Figure 60. Energy diagram for components [TMPyP-(L1)4]n and
TMPyP used to construct a photocell on an ITO glass electrode. (b)
Photocurrent responses of crystals of [TMPyP-(L1)4]n and [TMPyP-
(L2)2]n recorded in the presence of 0.1 M Na2SO4 aqueous solution.
(Reproduced with permission from ref 177. Copyright 2016 Royal
Society of Chemistry.)
Chart 6. Chemical Structures of TTF-Annulated
Porphyrazines
Syntheses of phthalocyanine derivatives are often accom-
plished through the self-condensation of phthalic acids,
phthalonitriles, or diiminoisoindole derivatives. These strategies
have been used to prepare TTF-Pcs. For instance, Decurtins and
co-workers reported195,196 a series of symmetrical TTF-
annulated Pcs along with their corresponding metal complexes
(61a−d in Chart 7). These systems were prepared by
macrocyclization of appropriately chosen TTF-annulated Pc
precursors in basic media (Scheme 33A). In this study, the
authors also demonstrated that those systems that bore long and
flexible aliphatic chains exhibited discotic liquid-crystalline
behavior; presumably, this reflects a cofacially stacked arrange-
ment of the extended and planar TTF-Pc cores.
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Review
The absorption spectra of 61d, recorded in THF in both its
neutral form and its tetraradical cationic state, are shown in
Figure 63a. It was demonstrated that the relatively broad Q-band
observed in the neutral form of 61d is due to aggregation
occurring in THF; in contrast, the sharper Q-band centered at
700 nm was ascribed to the monomeric species. In the case of the
symmetrical TTF-annulated Pcs, the emission is quenched in the
ground state. This quenching presumably reflects an efficient
intramolecular reductive electron transfer from the TTF subunits
to the Pc core. The emission intensity increases upon chemical
oxidation by FeCl3. Thus, these systems behave as efficient redox
switches. On the other hand, the neutral species 61a−d aggregate
rapidly in solution, which results in a quenching of the typical
phthalocyanine-based emissions at 710 and 786 nm. This aspect
of their chemistry might reduce the utility of systems such as 61
as molecular switches.
Electrochemical studies carried out by means of thin-layer
cyclic voltammetry revealed that all four TTF units in
compounds 61a−d are oxidized in two quasireversible steps
involving two four-electron oxidation processes. Within this
series, only the free-base form of 61a shows a reversible one-
electron reduction signal at −0.98 V vs Fc0/Fc+. This signal was
ascribed to reduction of the Pc core (Figure 63b). All other TTF-
annulated Pc derivatives are free of features under analogous
reduction conditions (see Table 11 for details).
After the initial reports by Decurtins and co-workers,195,196
Kimura and co-workers reported a series of symmetrical197−200
TTF-annulated Pcs containing soluble alkyl chains at the α-
positions (cf. compounds 63a and 63b in Chart 7, for example)
and used these compounds to investigate various substituent
effects. The synthesis of these species is shown in Scheme 33B.
Absorption spectral studies revealed a broad CT absorption band
that bears analogy to what is seen for various TTF-annulated
porphyrins (vide supra). This band is thought to originate from
partial electron transfer from the TTF subunits (donors) to the
Pc core (acceptor). Upon addition of iodine to these TTF-
annulated Pcs, the Q-band becomes significantly broadened and
undergoes a prominent red shift (Figure 63c). These spectral
changes were ascribed to the formation of an electron-transfer
complex displaying radical features.
Wang et al. reported201 another type of symmetrical thia-
crown-ether-TTF-functionalized Pc derivative. This compound,
64, was synthesized through the cyclotetramerization of the
corresponding thia-crown-ether-based phthalonitrile precursor
T (Scheme 33C). The absorption spectrum of 64 is characterized
by a TTF-based absorption band that overlaps with a broad Soret
band, a finding that was considered indicative of strong
aggregation in solution. Upon addition of TCNQ to this
compound, a sharp band appears at 400 nm, whereas the Q-band
remains intact (Figure 64a).
Electrochemical investigations of 64 revealed two oxidation
processes that do not apparently involve oxidation of the Pc core;
rather, the electrochemical processes in question appear to reflect
two separate four-electron oxidation processes associated with
the TTF units (Figure 64b and Table 11). A slight separation was
seen for the first oxidation wave that was thought to reflect an
interaction between the TTF•+ radical produced by oxidation
with neighboring TTF units, thus generating a species best
represented as [(TTF)2] •+.
To gain insight into the sensing capability for alkaline ions,
electrochemical analyses of 64 were carried out in the presence of
soluble (perchlorate) Na+, Li+, K+, and Cs+ cation salts. These
studies provided evidence of selectivity for the Na+ ion in that a
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Table 10. Electrochemical Data of Various TTF-Annulated Porphyrazines

compd Ered3 (V) Ered2 (V) Ered1 (V) Eox1 (V) Eox2 (V) Eox3 (V) Eox4 (V) ref
55a −1.760 −0.980 −0.490 +0.570 +0.910 +1.290 +1.630 183
55b − −1.190 −0.870 +0.440 +0.840 +1.130 +1.250 183
55c −1.790 −1.190 −0.830 +0.480 +0.840 +1.290 +1.860 183
56a − − − − − − − −
56ba − − −0.580 +0.670 +1.040 − − 180
56c − − − − − − − −
57ab − − −0.836 +0.998 +1.313 +1.784 − 182
57bb − − −0.802 +0.972 +1.304 +1.784 − 182
57cb − − −0.813 +0.914 +1.308 +1.786 − 182
58c − −1.177 −0.937 +0.544 +0.876 +1.189 − 185
59d − − −0.693 +0.563 +0.938 +1.218 − 190
a
Measurements were carried out in CH2Cl2/MeCN (5:1, v/v) containing 0.1 M TBAPF6 as the supporting electrolyte under an Ar atmosphere.
Platinum electrodes were used for the working and counter electrodes, and the reference electrode was Ag/AgCl. The scan rate was 100 mV s−1.
b
Measurements were carried out in CH2Cl2/MeCN (4:1, v/v) containing 0.1 M TBAPF6 as the supporting electrolyte under an Ar atmosphere.
Counter and working electrodes were made of Pt and glassy carbon, respectively; a calomel electrode (SCE) was used as the reference electrode. The
scan rate was 100 mV s−1. cMeasurements were carried out in CH2Cl2/MeCN (9:1, v/v) containing 0.1 M TBAPF6 as the supporting electrolyte
under an Ar atmosphere. Counter and working electrodes were made of Pt and glassy carbon, respectively; a calomel electrode (SCE) was used as
the reference electrode. The scan rate was 100 mV s−1. dMeasurements were carried out in CHCl3/MeCN (3:1, v/v) containing 0.1 M TBAPF6 as
the supporting electrolyte. The scan rate was 100 mV s−1. Potentials are reported against SCE.

Scheme 29. Synthetic Routes of Various Unsymmetrical and Symmetrical TTF-Annulated Porphyrazines

large positive shift in redox potential (ΔE1/21 = 80 mV) was seen
for Na+ by differential pulse voltammetry (DPV), whereas no
appreciable shifts were seen for the other alkali-metal ions tested
(e.g., Li+, K+, and Cs+). In this particular supramolecular system,
the redox properties of the TTF unit are combined with the
2691
complexing ability of the crown ether moieties to produce what
might emerge as a practical, electrochemical-based Na+ cation
sensor.
2.8.2. TTF-Crown-Ether-Functionalized Phthalocya-
nines. Nolte and co-workers reported classic thia-oxa-crown-
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Figure 61. (a) UV−vis−NIR spectral changes observed for a 2 × 10−5 M
CH2Cl2 solution of 57c upon the addition of 4 equiv of F4TCNQ. (b)
EPR spectrum of 57c recorded after mixing with F4TCNQ in CH2Cl2 at
room temperature. (Redrawn from data that were originally published in
ref 182.)
ether-fused metallophthalocyanines, as embodied in the
symmetric systems 65a and 65b.202,203 These systems were
found to self-assemble into helical tapes with nanometer widths
and lengths on the order of a few micrometers. These constructs
were found to display electron conductivity, ion-transport
features, and liquid crystallinity. The free-base form was
synthesized by tetracyclization of a TTF-thia-oxa-crown-ether-
annulated phthalonitrile precursor, U, whereas its Cu2+ complex,
65b, was synthesized from a diiminoisoindoline derivative of U
(i.e., V) using CuCl2 as a copper(II) cation source (Scheme 34).
Absorption spectral analyses of 65a were carried out in mixed
organic media consisting of various ratios of CHCl3 and MeOH.
These studies revealed that, as the concentration of MeOH was
increased, the Q-bands at 663 and 700 nm underwent a
hypsochromic shift eventually giving rise to a broad feature
centered at 630 nm at a 1:4 (v/v) ratio of CHCl3 to MeOH. This
spectral feature was considered indicative of 65a undergoing
Scheme 30. Synthetic Route Used to Prepare a TTF-Thia-Crown-Ether-Functionalized Porphyrazine
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Figure 62. (a) UV−vis−NIR spectral changes seen for a 1 × 10−5 M
CH2Cl2 solution of 58 upon the addition of 4 equiv F4TCNQ. (b) EPR
spectrum of 58 recorded in the presence of F4TCNQ in CH2Cl2 at room
temperature. (This figure was redrawn from data that were originally
published in ref 185.)
aggregation under these conditions (Figure 65a). Transmission
electron microscopy (TEM) revealed the formation of fibers of
up to several micrometers in length, which corresponds to stacks
of ca. 105 molecules (Figure 65b,c). A thorough inspection of the
fibers revealed the presence of a very thin bilayer-type motifs
(Figure 65b). These bilayers have widths on the order of 20 nm,
which corresponds to approximately 5 times the calculated width
of the individual molecules. From these observations and initial
modeling experiments, it was suggested that an unusual
combination of multiple TTF−TTF and TTF−Pc interactions
(as opposed to Pc−Pc interactions) underlie the supramolecular
self-association of 65a that leads to the formation of the higher-
order self-assembled scrolled molecular architectures. Both left
and right helices are observed (Figure 65c), as would be expected
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Scheme 31. Synthesis of Compound 59
Scheme 32. Synthetic Route Leading to TTF-Appended Pyrazinoporphyrazines
in the absence of any chiral bias associated with the aggregation
process.
2.8.3. TTF-Annulated Unsymmetrical Phthalocyanines.
Kimura and co-workers reported a series of unsymmetrical TTF-
annulated Pcs199,204−207 (compounds 66−70; Chart 8) that were
obtained from a mixture of two nonidentical phthalonitrile
derivatives. Photophysical, electrochemical, and surface chemical
studies were carried out to characterize these systems. The
general synthetic routes used to prepare the unsymmetrical Pcs
66−70 are summarized in Scheme 35.
Steady-state absorption spectral studies revealed that all of the
asymmetrically substituted Pcs 66−70 give rise to almost
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Review
identical absorption behaviors irrespective of the number of
TTF units attached to the central macrocyclic core. This finding
was rationalized in terms of π-electronic delocalization within the
neutral forms of these systems that is not strongly affected by the
outer functional groups (i.e., annulated to the isoindoline phenyl
groups). The addition of trifluoroacetic acid (TFA) to the TTF-
phthalocyanine 66a generated a cationic species and gave rise to a
new band centered at λmax = 740 nm (Figure 66) in the UV−vis−
NIR absorption spectrum.
Kimura and co-workers also demonstrated that unsymmetrical
TTF-fused Pcs, such as 70, would aggregate and that the alkyl
chains would pack closely within Langmuir−Blodgett (LB)
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Chart 7. Chemical Structures of Representative Symmetrical TTF-Annulated Phthalocyanines
films.204 In these films, the Pc ring planes are oriented
perpendicular to the water surface, whereas the long peripheral
alkyl chains extend into the air. The LB films constructed by 70
exhibit low conductivities in the range of 10−10−10−9 S cm−1 at
room temperature. Upon exposure of the LB films to I2 vapor,
their conductivities increased to 10−5−10−4 S cm−1, an effect
ascribed to the partial oxidation of the monomers within the LB
films.
2.8.4. Phthalocyanines Containing Peripheral TTF
Units Connected through Saturated Spacers. There are
numerous reports of Pc derivatives (Chart 9) wherein TTF units
are attached to the periphery of the macrocyclic core, using either
flexible saturated aliphatic linkers (e.g., 71−75)208−214 or axial
coordination to the Pc metal centers (e.g., 76).215
In general terms, these TTF-functionalized Pcs can be
considered as D−σ−A systems. They were thus expected to
act as a new generation of functional materials with interesting
solution-state and solid-state properties. They are also of interest
in terms of understanding the importance of various supra-
molecular interactions wherein redox-active groups are attached
to the highly conjugated planar Pc core in a dendritic fashion.
Cook et al. reported two unsymmetrically substituted discotic
liquid-crystalline Pcs (71 and 72) wherein TTF subunits are
attached to the periphery of the central macrocyclic core by long
and flexible alkyl chains.208 Compounds 71 and 72 were analyzed
using polarized light microscopy and differential scanning
calorimetry. It was observed that compound 71, with a single
TTF unit, exhibits a mesophase, tentatively assigned as Dhd based
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Review
on the fan-type birefringence texture observed under conditions
of polarized light microscopy. In contrast, incorporation of two
TTF units (as in 72) suppresses the mesophase formation. The
temperature range of the mesophase of 71, ca. 24 °C, is
significantly less than that of its precursor phthalocyanine (ca. 90
°C). Absorption spectroscopic analysis of spin-coated films of
these compounds revealed that their molecular architectures can
be modified by oxidation with iodine vapor or by heating.
Another class of metal-free phthalocyanine derivatives was
reported by Bryce and co-workers.209,210 The Pc systems in
question are symmetrically functionalized with eight (e.g., 73a,b)
or four (i.e., 74) peripheral TTF units. It was envisaged that the
presence of saturated alkyl-ether bridges would serve the dual
purpose of conferring some solubility on the system while
allowing the peripheral TTF units the conformational freedom
needed to achieve coplanarity with the Pc ring and form
intermolecular face-to-face stacks.
The synthesis of compounds 73a,b is shown in Scheme 36A. It
relies on a conventional high-temperature lithium pentoxide-
mediated macrocyclization reaction and involves the use of a
doubly TTF-substituted phthalonitrile synthon (DTTFPCN).
Compounds 73 and 74 display electrochemical properties
arising from both the TTF subunits and the phthalocyanine
cores. 1H NMR and UV−vis−NIR spectroscopic studies
provided evidence of their strong solvent-dependent aggregation
behavior. For instance, a hypsochromic shift in the Q-bands and a
broadening of the associated peaks was seen as the temperature
was lowered to 0 °C. This is consistent with the formation of
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Scheme 33. Synthetic Approaches to Symmetrical TTF-Annulated Phthalocyanines
cofacially aggregated Pcs at these lower temperatures. Upon
addition of iodine to the Pc-TTF constructs, broad CT bands
were observed at ≥800 nm, a finding considered to be consistent
with the formation of a TTF•+ radical species. Quenching of the
Pc-based emission was observed at ambient temperature;
presumably, this reflects CT interactions within these systems
that serve to deactivate the excited state.
Similar kinds of D−σ−A Pcs, bearing 4,5-ethylenedithio-TTF
(EDT-TTF) groups attached to the isoindoline subunits, were
reported by Shen and co-workers (75a−c).211−214 The synthetic
procedure is shown in Scheme 36B. The poor solubility of the
metal complexes complicated electrochemical analyses. Never-
theless, it was found that these Pc species exhibit two distinct
redox waves corresponding to oxidation of the TTF units. The
TTFs were found act as independent redox centers, as inferred
from the lack of electrochemical involvement of the Pc core
under the conditions of experiment.
A series of silicon phthalocyanine (SiPc) bis-esters was
reported by Beeby and co-workers. These systems, compounds
76a−e, rely on the use of two phenyl carboxylate ligands to ligate
the TTF units to the core Pc Si4+ center by axial coordination.215
Variations in the substitution patterns around the central
aromatic “hinge” within the ligands leads to different molecular
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Review
geometries. The authors demonstrated that the emission
properties of the SiPc core are quenched to varying degrees by
the axially coordinated electron-rich TTF subunits. The
magnitude of the quenching depends on both the relative
separation of the two redox-active components (Pc and TTF)
and the flexibility of the linking group. In the case of 76b
(containing a highly flexible linker group) and 76e (with a
dendritic axial ligand), the emission intensities of the macrocyclic
cores were reduced by 99% and 96%, respectively, relative to that
of a similar SiPc reference compound, W, lacking the TTF units.
Molecular modeling studies of these compounds provided a
framework for interpreting the degree of emission quenching in
terms of the intramolecular spacing. Varying the length of the
axial ligands in these complexes allowed the degree of quenching
of these TTF-functionalized Pcs to be tuned between 73% and
<1% relative to that of the reference system W. The strong
quenching observed in certain case s is consistent with facile and
rapid photoinduced electron transfer occurring within what are
formally coordination-based D−A ensembles.
The emission behavior of complexes 76 proved highly
temperature-dependent, with a sharp emission enhancement
being seen at the glass point of the solvent. This latter
observation was ascribed to the axial ligands being frozen into
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Figure 63. (a) UV−vis−NIR spectra of 61d recorded as a 2 × 10−6 M

solution in THF. (Note: The neutral form is shown with a line, whereas
a dotted line is used for the oxidized form.) (b) Representative thin-layer
CV of 61a in 0.1 M TBAPF6 in CH2Cl2/CH3CN (9.5:0.5 v/v) at a scan
rate of 100 mV s−1 using Pt electrodes. (Reproduced with the permission
from ref 195. Copyright 2005 American Chemical Society.) (c) UV−
vis−NIR spectra of compound 63b recorded in the absence and
presence of I2. (This figure was redrawn from data that were originally
published in ref 199.)
Figure 64. (a) UV−vis−NIR spectra of compound 64 in CH2Cl2
recorded before and after the addition of 1 equiv of TCNQ. (b) Change
in the DPV spectra of 64 recorded in CH2Cl2/MeCN (3:2, v/v)
observed upon the incremental addition of sodium perchlorate.
(Reproduced with permission from ref 201. Copyright 2008 Elsevier
Ltd.)

conformations wherein PET is blocked. PET could also be

blocked by oxidizing the TTF subunits, leading to the fluorescent
features being turned on. Support for the specific oxidation of the

Table 11. Electrochemical Data for Various TTF-Annulated Phthalocyanines

compd Ered3 (V) Ered2 (V) Ered1 (V) Eox1 (V) Eox2 (V) Eox3 (V) supporting electrolyte solvent ref
61aa
− − −0.98 +0.11 +0.62 − TBAPF6 DCM/MeCN 195
61ba − − − +0.14 +0.60 − TBAPF6 DCM/MeCN 195
61ca − − − +0.14 +0.60 − TBAPF6 DCM/MeCN 195
61da − − − +0.14 +0.59 − TBAPF6 DCM/MeCN 195
62ab − − − +0.16 +0.57 − TBAPF6 DCM 196
63a − − −1.29c +0.43d +0.73 − TBAClO4 DCM 198
63b − −1.36 −1.14 +0.39d +0.76 − TBAClO4 DCM 198
63ce − −1.48 −1.19 +0.42d +0.83 − TBAClO4 DCM 200
64f − − − +0.264 +0.592 − TBAClO4 DCM/MeCN 201
65bg − − − +0.75 +1.25 − TBAPF6 − 202
66ae − −1.39 −1.04 +0.41 +1.36 − TBAClO4 DCM 205
66b,ce − −1.30 −1.03 +0.38 +0.77 − TBAClO4 DCM 205
66de − −1.05 −0.79 +0.38 +0.73 − TBAClO4 DCM 205
67ae − −1.52 −1.18 +0.34d +0.69 − TBAClO4 DCM 207
67be − −1.42 −1.10 +0.44d +0.73 − TBAClO4 DCM 207
67ce − −1.42 −1.10 +0.44d +0.73 − TBAClO4 DCM 207
68ae −1.47d −1.27c −0.78d +0.41d +0.72d − TBAClO4 DCM 199
68be − −1.36c −0.98d +0.39d +0.73d − TBAClO4 DCM 199
69ae − −1.52 −1.18 +0.34d +0.69d − TBAClO4 DCM 199
69be − −1.75 −1.31 +0.33d +0.84d − TBAClO4 DCM 199
70e − − − +0.40 +0.60 +0.81 TBAClO4 DCM 204

a
Electrochemical potentials were measured in CH2Cl2/MeCN (9.5:0.5 v/v) using a Pt working electrode, and a scan rate of 100 mV s−1. Potentials
are in volts vs the Fc/Fc+ couple. bElectrochemical potentials were measured using a Pt electrode as the counter electrode. Potentials are in volts vs
Ag/AgCl. The scan rate was 100 mV s−1. cIrreversible. dQuasireversible. eElectrochemical measurements were carried out using a Ag/AgNO3 (0.01
M) reference electrode, a glassy carbon working electrode, and a Pt counter electrode at a scan rate of 200 mV s−1. fElectrochemical potentials were
recorded in CH2Cl2/MeCN (3:2, v/v) using a 5 × 10−4 M solution of 64. gElectrochemical measurements were carried out using a Ag/AgI reference
electrode and Pt working and counter electrodes. A scan rate of 100 mV s−1 was used.

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Scheme 34. Synthetic Scheme Leading to Symmetrical TTF-Crown-Ether-Functionalized Phthalocyanines
Figure 65. (a) UV−vis spectral change in the Q-bands of compound
65a observed upon the incremental addition of MeOH into initial
CHCl3 solutions. (b) TEM image of the gelated state of 65a showing its
fibrous structure. (c) TEM image of 65a showing the equal distribution
of both left-hand and right-hand helices. These helices have nanometer
widths and micrometer lengths. Scale bar = 200 nm. (Reproduced with
permission from ref 202. Copyright 2005 Royal Society of Chemistry.)
appended TTF subunits came from spectroelectrochemical
studies. Electrochemical data for all of the compounds discussed
in this section are summarized in Table 12.
2.8.5. Norphthalocyanines Attached to TTFs through
Saturated Spacers. TTF-Crown-Ether-Fused Norphthalocya-
nines. Tribenzoporphyrazines, or norphthalocyanines, are a class
of low-symmetry tetrapyrrolic macrocycles216−218 that represent
a special case of AB3 azaporphyrinic macrocyclic compounds in
which A represents a pyrrolic subunit and B is an isoindole
moiety. These products are typically obtained by means of
crossover cyclotetramerizations involving the use of phthaloni-
trile and maleonitrile precursors. Because of the two different
types of peripheral functionalities that result from these mixed
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Review
Chart 8. Chemical Structures of Some Representative
Unsymmetrical TTF-Annulated Phthalocyanines
condensations, the products obtained often exhibit unique
photophysical properties, including a strongly split Q-band
ascribed to π−π* transitions.
The introduction of a TTF unit onto the periphery of a
norphthalocyanine core imparts interesting optical and electro-
chemical properties that are presumably due to the combined
presence of a strong chromophore and a redox-active species
within a single molecular skeleton. Hou and co-workers reported
an AB3-type of norphthalocyanine (77a) and its Mg2+ complex
(77b), each of which bears a single TTF unit linked by a thia-
crown-ether spacer.219 To our knowledge, 77a and 77b represent
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Chemical Reviews
Scheme 35. Syntheses of Unsymmetrical TTF-Annulated Phthalocyanines
Figure 66. UV−vis−NIR spectral changes observed when the neutral
form of compound 66a is titrated with TFA in CHCl3. (Reproduced
with permission from ref 205. Copyright 2011 John Wiley & Sons.)
the only examples of TTF-annulated norphthalocyanines
reported to date. Their synthesis is shown in Scheme 37 and
involves as the key step the Mg2+-templated cross-cyclization of a
thia-crown-ether-based malonitrile precursor, X, with phthaloni-
trile at high temperature.
2698
Review
The ability of 77b to function as a potential donor for
F4TCNQ was demonstrated by the formation of a CT complex,
as evidenced by steady-state absorption, EPR, and IR
spectroscopic studies. Theoretical calculations provided further
support for the proposed intramolecular electronic interactions
within the TTF-bearing molecular construct (Figure 67).
Norphthalocyanines Connected to TTFs through Saturated
Thia-Ether Bridges. Compounds 78a and 78b, reported by Hou
et al., are norphthalocyanines bearing TTF subunits attached by
ethylenedithio spacers.220 The Mg(II) complex, 78b, was
synthesized by carrying out a mixed condensation between an
excess of phthalonitrile and precursor Y in n-butanol at reflux, in
accord with the conventional Mg(II)-template strategy. The free-
base form, 78a, was prepared by treating 78b with acid followed
by an aqueous workup (Scheme 38).
The optical spectra of the unsymmetrical norphthalocyanines
(NPcs) 78 recorded in CH2Cl2 are characterized by split Q-
bands that obey the Lambert−Beer law up to concentrations of
ca. 10 μM (Figure 68a). This finding was taken as evidence that
these compounds do not aggregate appreciably in CH2Cl2, THF,
or DMF at low concentrations; presumably, this reflects the long
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Chemical Reviews Review

Chart 9. Phthalocyanine Derivatives with Peripherally Tethered or Axially Coordinated TTF Units

Scheme 36. Synthetic Routes to Compounds 73a,b and 75b,c

To understand the electron-donor properties of these

alkyl (C12) chains present on the TTF units that serve to block compounds, electrochemical investigations were carried out in
intermolecular interactions. mixed solvents (CH2Cl2/MeCN, 9:1 v/v). The free-base form,
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Chemical Reviews Review

Table 12. Electrochemical Data for Phthalocyanines (V vs Fc/Fc+) Bearing Peripherally Fused or Axially Coordinated TTF Units
compd Ered2 (V) Ered1 (V) Eox1 (V) Eox2 (V) Eox3 (V) supporting electrolyte solvent scan rate mV/s ref
71b
− − +0.57 +0.73 +0.99 TEAClO4 DCM 100 208
72b − − +0.56 +0.70ir +0.92 TEAClO4 DCM 100 208
73ab −1.08 −0.74 +0.51 +0.83 − TEAPF6 DMF 1100 209
73bb − −0.51 +0.50 +0.87 +1.18 TBAPF6 BCN 100 210
74b − −0.50 +0.54 +0.92 +1.15 TBAPF6 DCM 100 210
75bc − − +0.620 +0.903 − TEABF4 DCM 12.5 214
75cc − − +0.612 +0.884 − TEABF4 DCM 12.5 214
76ab −1.36 −0.98 +0.23 +0.57 +0.78 TMABF4 DCM 20 215
77bd −1.42 −0.95 +0.47 +0.93 +1.59 TBAPF6 DCM/MeCN 100 219
78ae −1.566 −0.930 +0.476 +0.875 − TBAPF6 DCM/MeCN 100 220
78be −1.435 −1.000 +0.475 +0.863 +1.386 TBAPF6 DCM/MeCN 100 220
a
All measurements were carried out in the presence of 0.1 M supporting electrolyte as indicated and in the noted solvents under an Ar atmosphere.
b
Potentials are V vs the Ag/Ag+ reference and were recorded using Pt working and counter electrodes. cPotentials are reported against SCE.
d
Measurements were carried out in a 7:3 (v/v) mixture of CH2Cl2 and MeCN. ePotentials are reported against SCE in a mixture of CH2Cl2 and
MeCN (9:1 v/v). Note: TMA+ = tetramethylammonium cation.

Scheme 37. Synthesis of Unsymmetrical TTF-Crown-Ether-Fused Norphthalocyanines

properties of SubPcs bear analogy to those of Pcs but show

Figure 67. (a) HOMO and (b) LUMO contour surfaces of 77b.
(Reproduced with permission from ref 219. Copyright 2015 Elsevier
Ltd.)
78a, exhibits complex electrochemical features dominated by two
reduction signals ascribed to the norphthalocyanine core
(NPc−3/NPc−4 and NPc−2/NPc−3) and two oxidation signals
assigned to the TTF units (TTF•+/TTF and TTF2+/TTF•+)
(Table 12). However, in the case of the Mg(II) complex (78b), a
total of five redox signals are seen: two were assigned (Figure
68b) to NPc-based reductions 78a and three to oxidations,
assigned by the authors as TTF•+/TTF, TTF2+/TTF•+ and
NPc−1/NPc−2).
2.9. TTF-Annulated Subphthalocyanines
Subphthalocyanine (SubPcs) are ring-contracted phthalocyanine
analogues that contains a central coordinated boron atom.
SubPcs are synthesized readily and in good yields (in some cases
up to ∼90%) through the cyclotrimerization of phthalonitrile in
the presence of a boron trihalide reagent.221 The photophysical
2700
differences that might be expected given their relatively smaller
14 π-electron conjugation circuits. For instance, SubPcs typically
display an intense absorption band in the visible region (∼550
nm). The inherently bowl-shaped and C3 symmetric structures of
nonfunctionalized SubPcs allows a fine-tuning of their photo-
physical properties by varying their axial ligands. Modifying the
peripheral substituents provides another means of modulating
the basic properties of SubPcs.
Recognizing the potential benefits that could come from
functionalization of the SubPc core, Shimizu et al. reported a
series of TTF-annulated SubPcs.222 These products (79−81)
were synthesized through a conventional boron-templated
reaction involving tetrafluorophthalonitrile and a TTF-fused
phthalonitrile bearing thiomethyl substituents (Scheme 39).
All three possible TTF-annulated SubPcs (i.e., bearing one,
two, or three annulated TTF substituents) were found to display
features consistent with intramolecular charge transfer in analogy
to what was observed in the case of TTF-annulated Pcs as
discussed earlier in this review. All three TTF-annulated SubPcs
exhibit intense single Q-band absorption with a typical SubPc-
like shoulder that gradually broadens as the number of fused TTF
subunits increases from the mono-TTF SubPc, 79, through to
the triply fused TTF-SubPc, 81. Moreover, the Q-band gradually
shifts to lower energy, from 578 nm in the case of 79, to 584 nm
in the case of 80, and to 593 nm in the case of 81. Fluorescence
spectral studies of these TTF-SubPcs revealed a monotonic
quenching of the fluorescence intensity as the number of TTF
units annulated to the SubPc core increased. The quantum yield
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Chemical Reviews
Scheme 38. Synthesis of 78a,b
Figure 68. (a) UV−vis−NIR spectral changes observed upon varying
the concentration of 78b in CH2Cl2. Inset: Plot of the Q-band
absorption intensity at 697 nm vs concentration of 78b. (b) CV of 78b.
Inset: DPV of 78b recorded in 0.1 M TBAPF6 in a CH2Cl2/MeCN
mixture (9:1, v/v). (This figure was redrawn from data that were
originally published in ref 220.)
(Φf) determined for the mono-TTF-annulated system, 79, is
0.06. In contrast, the doubly fused SubPc system, 80, has a
fluorescence quantum yield (Φf) of 6.1 × 10−4, whereas no
detectable fluorescence emission was seen in the case of the tris-
TTF-annulated system, 81. The fluorescence quenching was
ascribed to the same intramolecular CT mechanism invoked for
other TTF-functionalized systems discussed in this review.
Chemical oxidation using Fe(ClO4)3 led to a concentration-
dependent increase in the intensity of the CT band located in the
2701
Review
∼650−1200-nm spectral range (Figure 69). As invoked in the
case of other TTF-functionalized chromophores, this relative
increase in fluorescence was ascribed to oxidation of the TTF
units and a commensurate decrease in their ability to act as
electron donors.
Electrochemical investigations of these TTF-annulated
SubPcs carried out in o-dichlorobenzene revealed two oxidation
potentials (vs Fc0/Fc+) for each species. The integrated
intensities of the individual redox waves gradually increased as
the number of TTF substituents attached to the SubPc core
increased (Table 13). This finding is consistent with the notion
that these oxidation processes are largely TTF-centered.
3. CONCLUSIONS AND FUTURE PROSPECTS
The parent TTF-annulated pyrroles were first reported 17 years
ago. Studies of TTF-fused oligopyrrolic macrocyclic systems
started shortly thereafter and then blossomed rapidly. Currently,
a large variety of pyrrolo-TTF macrocyles are known, including
TTF-calixpyrroles, TTF-porphyrins, TTF-phthalocyanines,
TTF-subphthalocyanines, and TTF-porphyrazines, to name a
few prominent systems. In this review, we have discussed how the
photophysical and electrochemical sensing behaviors of the core
systems are affected by annulation or tethering of TTF
substituents. Typically, substantial differences in the charge-
transfer (CT) behavior, the electrochemical properties, and the
excited-state dynamics are observed. In some cases, the effects of
TTF functionalization on the metal-free and corresponding
metal-complexed forms differ significantly. This subtlety has
allowed for control over both the ground- and excited-state
properties and for the development of new ET systems. Anion-
induced conformational changes and cooperative guest-binding
properties of TTF-pyrrolic macrocycles (i.e., calix[n]pyrrolic
hybrids) have also been exploited as a means of controlling the
electronic features of TTF-based macrocyclic systems. This
control, in turn, has allowed for the development of sensors and
has provided a means to modulate the nature and extent of
electron transfer.
Of particular interest are TTF-based systems bearing photo-
responsive chromophores, such as porphyrins, porphyrazines,
and phthalocyanines. Several of these constructs have demon-
strated utility in terms of effecting solar energy conversion or
capturing and storing charges at the molecular level. The
progress made has obvious ramifications in terms of mimicking
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Chemical Reviews
Scheme 39. Synthesis of TTF-Annulated Subphthalocyanines
Figure 69. UV−vis−NIR spectral changes seen when the TTF-
annulated SubPc 81 is subjected to chemical oxidation by Fe(ClO4)3 in a
CHCl3/MeCN mixture (2:1 v/v). (Reproduced with permission from
ref 222. Copyright 2013 Wiley-VCH Verlag GmbH.)
Table 13. Electrochemical Data for TTF-Annulated
Subphthalocyanines
compd Ered1 (V) Eox1 (V) Eox2 (V)
79 −1.49 +0.20 +0.48
80 −1.56 +0.22 +0.43
81 −1.43 +0.16 +0.39
a
Measurements were carried out in o-dichlorobenzene containing 0.1
M TBAClO4 as the supporting electrolyte under an Ar atmosphere.
Potentials are in volts vs the Fc/Fc+ couple recorded under the
conditions of analysis. The scan rate was 100 mV s−1.
artificial photosynthesis and advancing solar cell applications.
TTF-functionalized oligopyrrole systems have also proved useful
in terms of supporting self-assembly and effecting sensing,
particularly for electron-deficient substrates. In both of these
broad application areas, challenges remain. For instance,
improvements in solar cell performance could be envisioned if
one could learn to control more precisely the dimensional
engineering of well-defined self-assembled nanoarchitectures by
using TTF-based interactions to align molecular dipoles, to
control more precisely molecular electronics, and to establish
and maintain orbital symmetries. Separately, an ability to
engineer the controlled disassembly of aggregated TTF-
pyrrole-based systems could allow for the construction of ever
more sensitive sensors for nitroaromatic explosives, as well as
potentially a range of other substrates. Systems containing
multiple TTF units could also emerge as promising charge-
storage devices and might lead to new types of electrode
materials suitable for use in batteries. In particular, TTF
2702
Review
derivatives could emerge as potential redox mediators in
nonaqueous Li−O2 batteries and might permit enhanced
recharge kinetics and greater cycle reversibility. Here, the ion-
responsive nature of many of the TTF-containing oligopyrrolic
constructs detailed in this review could contribute to effective ion
and charge transport. It is thus our prediction that materials
based on TTF-containing oligopyrrole precursors will continue
to enhance our fundamental understanding while driving
advances across a number of application areas. It is our hope
that the present review, which was deigned to summarize the
current state of the art, will inspire efforts along both of these
lines.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: joj@sdu.dk. Tel.: +45-6550-2587.
*E-mail: sessler@cm.utexas.edu. Tel.: +1-512-471-5009.
Notes
The authors declare no competing financial interest.
Biographies
Atanu Jana received his Ph.D. in Supramolecular Chemistry from the
Indian Institute of Technology Kanpur, India, in 2010 under the
supervision of Professor Parimal K. Bharadwaj. His first postdoctoral
research experience was with Professor Jonathan L. Sessler at Yonsei
University (Seoul, South Korea) under the support of a World Class
University (WCU) research program led by Prof. Dongho Kim. After his
time in Seoul, Dr. Jana moved to the National Institute for Materials
Science (NIMS), Tsukuba, Japan, and worked with Dr. Jonathan P. Hill
and Professor Katsuhiko Ariga before joining Professor Michael D.
Ward’s Group at the University of Sheffield, U.K., as a European
Commission Marie Curie International Incoming Research Fellow
(2013−2015). His current research interests focus on various
macrocyclic materials constructed using, among others, crown ether,
cryptand, TTF-calixpyrrole, and TTF-porphyrin building blocks, as well
as studies of their properties, supramolecular charge-transfer phenom-
ena, guest recognition, and biological and medicinal applications.
Masatoshi Ishida received his Ph.D. degree from Kyushu University in
2010 under the supervision of Professor Yoshinori Naruta. After
working as a research fellow at the Institute for Materials Chemistry and
Engineering (IMCE), Kyushu University, he worked with Professors
Jonathan L. Sessler and Dongho Kim as a WCU postdoctoral research
fellow at Yonsei University (Seoul, South Korea). He is currently an
Assistant Professor in the Department of Chemistry and Biochemistry
and Center for Molecular Systems (CMS) at Kyushu University
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Chem. Rev. 2017, 117, 2641−2710
Chemical Reviews Review

(Fukuoka, Japan). His current research interests are focused on the Republic of Korea. S.B. gratefully acknowledges The Danish
synthetic and redox chemistry of novel π-conjugated porphyrinoids. Council for Independent Research, Technology, and Production
Jung Su Park received his Ph.D. from The University of Texas at Austin Sciences (FTP, Project 5054-00052). J.O.J. thanks the Villum
in 2010 under the supervision of Professor Jonathan L. Sessler. He then Foundation and the Danish Natural Science Research Council
worked with Professor Chad Mirkin as a postdoctoral research fellow at (FNU, Project 11-106744) for financial support. J.L.S. acknowl-
Northwestern University (Evanston, IL). He is presently an Assistant edges the U.S. National Science Foundation (Grant CHE-
Professor in the Department of Chemistry at Sookmyung Women’s 1402004), the Robert A. Welch Foundation, and the Korean
University (Seoul, South Korea). His current research focus involves the World Class University Program for support of this work.
development of responsive organic functional materials based on redox-,
photo-, and chemically responsive organic building blocks. ABBREVIATIONS
Steffen Bähring received his Ph.D. in Supramolecular Chemistry from
BArF− tetrakis[bis(3,5-trifluoromethyl)phenyl]borate)
anion
the University of Southern Denmark (Odense, Denmark) in 2013 under
BHEEN 1,5-bis[(2-hydroxyethoxy)ethoxy]naphthalene
the guidance of Professors Kent A. Nielsen and Jan O. Jeppesen. While
BIQ bisimidazolium quinine (1,3,5,7-tetramesityl-4,8-
working on molecular sensors incorporating tetrathiafulvalene-calix[4]-
dioxo-3,4,7,8-tetrahydrobenzo[1,2-d:4,5-d′]-
pyrrole, he joined the group of Professor Jonathan L. Sessler for a
diimidazole-1,5-diium)
research stay during 2011−2012. After the awarding of his Ph.D., he
BTTF-C4P benzo-TTF-calix[4]pyrrole
worked at the Danish Technological Institute. During this period, he
C[4]P calix[4]pyrrole
focused on supporting research and development efforts for Danish
CD β-cyclodextrin
industry, with a particular emphasis on oil and gas. He is currently a
CHCl3 chloroform
Danish Independent Postdoctoral Researcher in the groups of
CPK Cory−Pauling−Koltun
Professors Jeppesen, Sessler, and Guldi, where he is working on organic
CS charge-separated
photovoltaics based on tetrathiafulvalene.
CT charge-transfer
Jan O. Jeppesen received his B.Sc., M.Sc., and Ph.D. degrees in 1996, CV cyclic voltammogram
1999, and 2001, respectively, from the University of Southern Denmark C60 fullerene
(Odense, Denmark) for work in supramolecular tetrathiafulvalene CBPQT4+ cyclobis(paraquat-p-phenylene)
chemistry. In the first part of his Ph.D. studies, he developed a synthetic DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
route to pyrrolo-tetrathiafulvalenes, and in 2000−2001, he joined the DCE 1,2-dichloroethane
group of Professor J. Fraser Stoddart at the University of California, Los DCM dicholoromethane
Angeles (UCLA), working on the design and synthesis of amphiphilic DDQ 2,3-dichloro-5,6-dicyano-1,4-quinolene
bistable [2]rotaxanes. He is the recipient of several research prizes DFT density functional theory
including the Ellen and Niels Bjerrum Chemistry Award (2014), the DLS dynamic light scattering
Torkil Holm prize (2010), the Villum Kann Rasmussens award (2009), DMSO dimethyl sulfoxide
the Aksel Tovborg Jensens award (2009), the Bjerrum−Brøndsted− DMF N,N-dimethylformamide
Lang lectureship (2009), and the Hede Nielsens prize (2003). He is a DNP-C4P bis-dinitrophenyl-calix[4]pyrrole
member of the Executive Committee of The Danish Council for DNT 2,4-dinitrotoluene
Independent Research, Technology, and Production Sciences (FTP). DONP dioxynaphthalene
Since 2008, Jan O. Jeppesen has been a Full Professor at the University DOSY-NMR diffusion-ordered NMR
of Southern Denmark, and he is one of the world’s leading scientists in DPV differential pulse voltammetry
the areas of synthetic and supramolecular chemistry of tetrathiafulva- DVD digital versatile disc
lenes. Home page: http://www.jojgroup.sdu.dk. EDT-TTF 4,5-ethylenedithiotetrathiafulvalene
Jonathan L. Sessler received a B.Sc. degree in Chemistry in 1977 from EPR electron paramagnetic resonance
the University of California, Berkeley. He obtained his Ph.D. from ET electron transfer
Stanford University in 1982. He was an NSF-NATO and NSF-CNRS F4TCNQ 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodime-
Postdoctoral Fellow at Université Louis Pasteur de Strasbourg (1982− thane
1983). In 1984, he accepted a position as an Assistant Professor of HOMO highest occupied molecular orbital
Chemistry at the University of Texas at Austin, where he is currently the ICT intramolecular charge transfer
Doherty-Welch Chair. Professor Sessler was also a WCU Professor at IPCE incident photon-to-current efficiency
Yonsei University in Seoul, South Korea. He recently accepted a IR infrared
summer research professorship and laboratory directorate at Shanghai ITC isothermal titration calorimetry
University. Professor Sessler is one of the world’s leading scientists LB Langmuir−Blodgett
working in the areas of supramolecular chemistry and expanded LUMO lowest unoccupied molecular orbital
porphyrin chemistry. Home page: http://sessler.cm.utexas.edu/Home. MALDI-TOF matrix-assisted laser desorption ionization time-
html. of-flight
MeCN acetonitrile
MO molecular orbital
ACKNOWLEDGMENTS MSA methanesulfonic acid
A.J. gratefully acknowledges a Marie Curie International NDI naphthalenediimide carboxylate
Incoming Fellowship (MC-IIF). M.I. acknowledges a JSPS NIR near-infrared
Grant-in-Aid for scientific research (No. 16K05700). J.S.P. is NMR nuclear magnetic resonance
grateful for support under a “Cooperative Research Program for NMF N-methylfulleropyrrolidine
Agriculture Science & Technology Development (Project NPc norphthalocyanine
PJ010506)” grant from the Rural Development Administration, OTE optically transparent electrode
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Chemical Reviews Review

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2710 DOI: 10.1021/acs.chemrev.6b00375

Chem. Rev. 2017, 117, 2641−2710