Article

pubs.acs.org/accounts

Lanthanide-Functionalized Metal−Organic Framework Hybrid

Systems To Create Multiple Luminescent Centers for Chemical
Sensing
Bing Yan*
School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, China

CONSPECTUS: Metal−organic frameworks (MOFs) possess an

important advantage over other candidate classes for chemosensory
materials because of their exceptional structural tunability and
properties. Luminescent sensing using MOFs is a simple, intuitive,
and convenient method to recognize species, but the method has
limitations, such as insufficient chemical selectivity and signal loss.
MOFs contain versatile building blocks (linkers or ligands) with
special chemical reactivity, and postsynthetic modification (PSM)
provides an opportunity to exploit and expand their unique
properties. The linkers in most MOFs contain aromatic subunits
that can readily display luminescence after ultraviolet or visible
(typically blue) excitation, and this is the main luminescent nature of
most MOFs. The introduction of photoactive lanthanide ions (Ln3+)
into the MOF hosts may produce new luminescent signals at different
positions from that of the MOF linker, but this depends on the intramolecular energy transfer (antenna effect) from the MOF
(linkers) to the Ln3+ ions. Controlling the Ln3+ content in MOF hybrids may create multiple luminescent centers. The nature of
the unique luminescent centers may cause different responses to sensing species (i.e., ratiometric sensing), which may provide a
new opportunity for luminescence research with applications to chemical sensing.
In this Account, recent research progress on using lanthanide-functionalized MOF hybrid materials to create multiple
luminescent centers for chemical sensing is described. Here we propose a general strategy to functionalize MOF hosts with
lanthanide ions, compounds, or other luminescent species (organic dyes or carbon dots) and to assemble types of
photofunctional hybrid systems based on lanthanide-functionalized MOFs. Five main methods were used to functionalize the
MOFs and assemble the hybrid materials: in situ composition, ionic doping, ionic exchange, covalent PSM, and coordinated
PSM. Through the lanthanide functionalization, multiple (double or triple) luminescent centers were created with different
luminescent bands in the visible region. Because of the different luminescent natures of the lanthanide ions, MOF linkers, and
other species (organic dyes or carbon dots), they display different responses to sensing species. Currently, using these strategies,
we have utilized a dual-response luminescent probe to realize chemical sensing of different types of cations (Fe3+/Fe2+, Hg2+, and
Cd2+), anions (Cr2O72−/CrO4− and CO32−), molecules (volatile organic compounds and O2), special air pollutants
(formaldehyde), and biomarkers of food spoilage as well as pH and temperature. Additionally, we have achieved triple-
luminescence-response sensing of ions (Ag+, Hg2+, and S2−) in complicated aqueous environments, which was developed using a
logic operation.

1. INTRODUCTION comes from five components in MOFs,8 and the luminescence

Metal−organic frameworks (MOFs) or porous coordination
polymers (PCPs) have caused a renaissance in coordination
chemistry because of their simple synthesis and versatility that
originates from their organic linkers. The highly porous and
crystalline frameworks of MOFs endow them with suitable
properties or functions for practical applications.1−5 MOFs can
undergo late-stage transformations without compromising the
overall framework integrity, and a variety of chemical reactions
are available to modify the framework components. Post-
synthetic modification (PSM) of MOFs is broadly defined as
the chemical derivatization of MOFs after their formation.6,7
With both organic ligands and metal ions, MOFs exhibit a
wide range of emissive phenomena. Luminescence mainly
of the linkers and metal ions is the most important and
extensive. The luminescence from groups on linkers or ligands
can be emitted directly from the linker or can involve charge
transfer with coordinated metal ions or clusters. Framework
metal ions can cause a pronounced increase in the
luminescence intensity through an antenna effect, e.g.,
lanthanide ion (Ln3+) MOF systems. MOFs offer a unique
platform for luminescent materials because they have a degree
of structural predictability and well-defined environments for
luminophores in a crystalline state.9
Received: August 4, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.accounts.7b00387

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These features allow for the development of photofunctional
hybrid materials based on Ln3+-functionalized MOFs. When
Ln3+ ions are introduced to functionalize a MOF host, they
provide multiple (mainly dual) luminescent centers in the
hybrid systems that emit at different positions in the visible
region. Generally, the luminescence from linkers occurs in the
blue or violet region with a narrow wavelength, but photoactive
lanthanide ions, especially Eu3+, emit in the red region with a
long wavelength, which allows for luminescence tuning and
white-light integration for practical applications in lighting or
displays. The different luminescent natures of these species
(linkers, Ln3+, or other species) also result in different
responses, which are useful for chemical sensing, especially
ratiometric sensing.
In this Account, a general strategy is proposed to create
multiple luminescent centers by Ln3+ functionalization of MOF
hosts to create hybrid systems for chemical sensing (Figure 1).
Figure 1. Scheme for the strategy to assemble lanthanide-function-
alized MOF hybrid systems for chemical sensing.
Here dual-luminescent centers are mainly used, and Eu3+ is the
most important lanthanide ion because of its bright red
emission. For triple-luminescent centers, two different
lanthanide ions (e.g., Eu3+ and Tb3+) are both introduced
into the MOF units via a simple process. A more extensive
method can be used to assemble other photoactive species
(organic dyes or carbon dots). Thus, chemical sensing research
can be performed by examining the responses of the different
luminescent centers to various sensing species.
2. FUNCTIONALIZATION PATHS
Lanthanide-ion-functionalized MOFs as photofunctional hybrid
systems can be created via several methods, and the method
depends on the MOF host. According to our research and
other relevant work, five main methods are used for different
interactions between Ln3+ ions and MOFs (Figure 2).
2.1. In Situ Composition
Lanthanide compounds can be assembled with MOF hosts
through an in situ solvent dispersion process, which is
physically composed to keep the whole luminescent hybrid
system stable. Here we select zeolitic imidazolate frameworks
(ZIFs) with special imidazole derivative linkers as an
example.10−12 Liu and Yan13 assembled surfactant-capped
nanoparticles (NaYF4:Yb3+, Er3+/Tm3+) with ZIF-8 through
the in situ composition method. Under excitation with a 980
nm diode laser, the NaYF4:Yb3+/Er3+@ZIF-8 and NaYF4:Yb3+/
Tm3+@ZIF-8 nanocomposites emitted yellow-green and light-
violet-white colors, respectively. Under near-ultraviolet (NUV)
excitation at 396 nm, both nanocomposites displayed a blue
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Figure 2. Scheme for the five main paths to assemble luminescent
lanthanide-functionalized MOF hybrids, with typical MOFs shown in
parentheses.
emission at 450 nm. Through selective excitation, up- and
downconversion luminescence was obtained. Duan and Yan14
embedded zinc oxide into MOFs (ZnO@Zn(pdc), pdc = 2,5-
pyridinedicarboxylate). Upon the formation of ZnO, the
morphology of the hybrid system changed. Moreover, Eu3+-
activated MOFs were obtained and displayed white-light
emission through a dual-emitting pathway (Eu3+ ion and
ZnO), and the fabricated white-light-emitting diode (WLED)
had CIE and correlated color temperature (CCT) values of
(0.35, 0.41) and 5018 K, respectively.
2.2. Ionic Doping
For lanthanide MOFs, ionic doping is the first choice to
assemble lanthanide-ion-functionalized MOF hybrids. Duan
and Yan15 prepared MOF-76(Y):Ln hybrids via ionic doping of
MOF-76 developed by Yaghi’s group.16 The photoluminescent
color of MOF-76(Y):10 mol % Eu3+/10 mol % Tb3+ could be
tuned from yellow to yellow-green, warm white, and orange by
changing the excitation wavelength of 300−380 nm. The
surface of a NMOF-76:Eu3+ polymer film was smooth,
continuous, and transparent under sunlight.15 Lian and Yan17
further prepared a series of MOF-76(Ln) compounds using the
ionic doping approach and evaluated their adsorption ability for
different dyes. The samples soaked in cationic dyes were dyed
blue, red, violet, and pink, but the samples soaked in the anionic
dyes remained colorless. The selective adsorption of different
dyes was due to the interactions between the dye molecules and
the frameworks, which could be used to develop an adsorbent
to remove cationic dyes from aquatic environments.
2.3. Ionic Exchange
Many anionic MOF systems with dimethylammonium (DMA)
cations in their porous structure exist, and other cations,
including metal ions, can be introduced into the MOF via ionic
exchange with DMA. For example, Bio-MOF-1
(Zn8(ad)4(BPDC)6O·2Me2NH2, ad = adeninate, BPDC =
biphenyldicarboxylate) was functionalized via postsynthetic
cation exchange of luminescent lanthanide ions by An et al.,18
and visible (Tb3+, Sm3+, and Eu3+) and NIR (Yb3+) emissions
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Figure 3. (a) Temperature-dependent emission spectra of Eu3+@UiO-bpydc. (b) Intensity ratio of bpydc (530 nm) to Eu3+ (614 nm) as a function
of temperature. (c) Temperature dependence of the luminescence lifetime of Eu3+. (d) Thermometric response curve plotting the back energy
transfer rate (KBEnT) vs temperature. (e) Arrhenius plots for KBEnT of Eu3+@UiO-bpydc. Reproduced with permission from ref 40. Copyright 2015
Royal Society of Chemistry.
within the MOF pores were observed.19 Shen and Yan20
introduced 2-thenoyltrifluoroacetone (TTA) to the Eu3+ (or
Eu3+/Tb3+)-exchanged Bio-MOF-1 via the “ship-in-bottle”
method. The introduction of the TTA ligand to the Eu3+@
Bio-MOF-1 hybrid system improved the luminescence intensity
of Eu3+, and the emission intensity of the Bio-MOF barely
changed. The emission spectrum of double lanthanide ion
(Eu3+/Tb3+)-functionalized Bio-MOF-1 hybrids showed CIE
coordinates close to the white region. Zhao et al.21 presented an
anionic MOF, {[Me2NH2]0.125[In0.125(H2L)0.25]·xDMF}n (H4L
= 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid), and used
Ln3+-modified MOF hybrids as potential luminescent probes
for Ln3+ ions.
2.4. Covalent Postsynthetic Modification
The aim of covalent postsynthetic modification of MOFs is to
create coordination groups of linkers in MOFs to further
coordinate lanthanide ions. Abdelhameed et al.22,23 used the
isoreticular MOF IRMOF-3 because of its noncoordinating
amino groups on the benzenedicarboxylate linker, which could
be easily modified by nucleophilic substitution, nucleophilic
addition, or reductive amination and subsequently coordinated
with Ln3+ ions. The second aromatic ring on the β-diketonate
as an assistant ligand could further enhance the Ln3+ sensitivity.
Lian and Yan24 prepared lanthanide hybrids containing both
MOFs and SBA-15 (a hexagonal mesoporous silica structure)
using the covalent postsynthetic modification path. SBA-15 is
easily modified by a cross-linking reagent to form Si-SBA-15,
and IRMOF-3 could be covalently grafted to Si-SBA-15
through an addition reaction. Finally, lanthanide ions were
introduced into the SBA-15-Si-IRMOF-3 host via a coordina-
tion reaction, and the resultant product exhibited the
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characteristic luminescence of Ln3+ in both the visible and
NIR regions.
2.5. Coordinated Postsynthetic Modification
If the linkers in MOFs possess free coordinating groups during
the construction of MOF systems, they provide a position to
react with lanthanide ions. Some typical linkers include 2,2′-
bipyridine-5,5′-dicarboxylic acid (H2bpydc) and multiple
carboxylic acids. H2bpydc possesses two free bipyridine N
atoms and forms a typical MOF, MOF-253,25 which can be
coordinated to Ln3+ to realize the PSM.26 Lu and Yan27
prepared a MOF-based monolayer luminescent thin film by
encapsulating lanthanide ions into a fabricated MOF (MOF-
253) host and then introducing a second ligand, TTA or 1,1,1-
trifluoropentane-2,4-dione (TAA), to sensitize the incorporated
Ln3+ ions. Additionally, they introduced multiple visible-
emitting Ln3+ ions (Eu3+, Tb3+, and Sm3+) to MOF-253 via
PSM for barcoding.28 The luminescence intensities of two
lanthanide ions could be quantitatively controlled and reflected
as a unique visible color corresponding to three distinct
barcodes. Research work could be extended to other MOFs
with similar linkers.29,30 For example, a thin layer of Eu3+@
MOFUiO-67-bpydc was coated onto a commercially available
UV-LED chip, and upon illumination, the chip generated bright
white light with CIE and CCT values of (0.3481, 0.3292) and
4914 K, respectively. The color rendering index (CRI) was 75,
and the luminous efficiency of the fabricated LED was 32 lm
W−1.30 Other typical MOFs for PSM were an Al-MIL-53
derivative31 and its analogues with a noncoordinating carboxyl
group.32−36 Zhou and Yan32 introduced Ln3+ cations into the
pores of Al-MIL-53-COOH. The emission colors were
modulated from blue to white to red. They prepared a
transparent, continuous, and homogeneous thin film of Eu3+@
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Figure 4. (top) Scheme of MOF-253 modified by the Eu3+ complex with TTA, with two types of Eu3+ (Eu1 and Eu2). (bottom) (a, b) Emission
spectra of MOF-253-Eu-TTA in aqueous solutions with different pH with (a) λex = 330 nm and (b) λex = 375 nm (b); (c) linear variation of the 5D0
→ 7F2 emission intensity ratio (Ir) of the two types of Eu3+. Reproduced with permission from ref 41. Copyright 2014 Royal Society of Chemistry.

Figure 5. (a) PL spectra of Eu3+@MIL-124 dispersed into different aqueous solutions of various metal ions (10−2 mol L−1). The inset shows the
spectra of Fe2+ (black line) and Fe3+ (red line). (b) Luminescence intensities of the 4D0 → 7F2 transition of Eu3+@MIL-124 interacting with different
metal ions in 10−2 mol L−1 aqueous solutions of MCln (λex = 298 nm). The inset shows the corresponding photographs under UV irradiation at 254
nm. Reproduced from ref 36. Copyright 2014 American Chemical Society.

Al-MIL-53-COOH, which showed white-light emission under
350 nm excitation. Xu and Yan 3 6 used MIL-124
(Ga2(OH)4(C9O6H4)) to construct hybrids with Ln3+ cations,
and the hybrids showed the luminescent properties of both the
Ln3+ ions and the linker. In addition, Cao et al.37 prepared
Ln3+-exchanged MOFs to sensitize Tb3+.
3. CHEMICAL SENSING
This section focuses on lanthanide-ion-functionalized MOFs as
hybrid systems with other photoactive species and the use of
their multiple luminescent centers for chemical sensing.
Luminescent centers may have different responses to sensing
species based on their luminescent nature. For example, the
luminescence intensity can show contrary changes (quenching
or enhancement), resulting in ratiometric sensing. Dual-
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response luminescence is the most popular, and herein we
mainly focus on chemical sensing with dual-luminescent
centers.
3.1. Thermometer
Ratiometric sensing based on two different luminescent centers
can be used as a thermometer, which is based on MOF hosts
cofabricated with two lanthanide ions (Eu3+ and Tb3+). As a
result of energy transfer from Tb3+ to Eu3+, the MOFs have
different luminescence intensities as the temperature changes.
In addition, this technique does not require additional
calibration of the luminescence intensity. Rao et al.38 first
created a mixed lanthanide MOF thermometer, Tb0.9Eu0.1PIA
(PIA = 5-(pyridin-4-yl)isophthalate), which exhibited a
significantly different temperature-dependent luminescent
behavior compared with the emissions of Eu3+ at 615 nm and
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Figure 6. (a) Linear relationship between IEu/ICD and CHg2+ (λex = 360 nm). The inset shows photographs of the test plates treated with different
concentrations of Hg2+. (b) Comparison of the PL intensity ratio IEu/ICD for Eu3+/CDs@MOF-253 dispersed in aqueous solutions of metal ions.
Reproduced with permission from ref 43. Copyright 2016 Royal Society of Chemistry.

Figure 7. (a) Emission spectra and (b) IL/IEu intensity ratios of Eu3+@UiO-bpy after the encapsulation of VOCs. (c) 2D decoded map of the
aromatic VOCs based on the emission intensity ratio (IL/IEu) and quantum yield (Φ) responses of the Eu3+@bpy-UiO nanocomposite. Reproduced
with permission from ref 46. Copyright 2016 Royal Society of Chemistry.

Figure 8. (left) Values of the luminescence intensity ratio (IEu/IL) for coated NMOFs@O-PP films under repeated cycles of 1 atm O2 and 1 atm N2
conditions with λex = 395 nm. (right) Photographs of a 395 nm LED modified by coating with NMOFs@O-PP and emission spectra of the coated
NMOFs@O-PP under (a) 100% N2 and (b) 100% O2. Reproduced with permission from ref 47. Copyright 2016 Royal Society of Chemistry.

Tb3+ at 546 nm. From 100 to 300 K, the emission intensity of
Tb3+ decreased while that of Eu3+ increased, and the
temperature-dependent luminescence colors could be tuned
from green to yellow. Zhou et al.39 discovered the temperature
sensing potential of Ln3+@In(OH)(bpydc) hybrids obtained by
Eu3+/Tb3+ coordinated PSM. The ratiometric thermometric
parameter of Eu3+/Tb3+@In(OH)(bpydc) was defined as the
ratio of the intensities of the 5D4 → 7F5 (Tb3+, 545 nm) and
5
D0 → 7F2 (Eu3+, 613 nm) transitions (ITb/IEu). The thermal
E DOI: 10.1021/acs.accounts.7b00387
sensitivity of Eu3+/Tb3+@In(OH)(bpydc) in MOF nano-
thermometers was high (4.97% °C−1).
Zhou and Yan40 also examined the feasibility of Eu3+@UiO-
bpydc for ratiometric thermometry (Figure 3a,b). When the
temperature increased, the Eu3+ emission intensity decreased
while the ligand-centered emission significantly increased,
which was attributed to the back energy transfer (BEnT)
from Eu3+ cations to bpydc linkers. The temperature-dependent
emission lifetimes (Eu3+) of the MOF hybrids were recorded to
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Figure 9. (a) Fluorescence intensities (IEu, IL, and IEu/IL) of Ag+/Eu3+@UiO-66 films after treatment with various indoor polluting gases. (b)
Concentration-dependent intensities IEu and IL. (c) Dependence of IEu/IL on the FA concentration. Reproduced with permission from ref 51.
Copyright 2016 Royal Society of Chemistry.
Figure 10. (top) Schematic diagrams of MOF-to-ZnO energy transfer
in ZnO@UiO-MOF heterostructures and the sensing mechanism
toward aldehydes over ZnO. (bottom) PL intensities (I614 and I470) of
Eu3+@ZUM test paper after exposure to various polluting gases in
vehicles (λex = 365 nm). Reproduced with permission from ref 52.
Copyright 2017 Royal Society of Chemistry.
determine KBEnT and the activation energy, Ea (Figure 3c). The
calculated KBEnT increased with increasing temperature (Figure
3d). The slope of the Arrhenius plots for KBEnT was 1.98, which
resulted in a value of 44 kJ mol−1 for Ea (Figure 3e). To
quantitatively determine the temperature sensing function of
Eu3+@UiO-bpydc, the ratiometric parameter was defined as the
ratio of the intensities of the dual 530 nm (bpydc) emission to
the 614 nm (Eu3+) emission (I530/I614).
3.2. pH
Eu3+ can be controlled to produce a dual-emission center.
Although the emission position is the same for Eu3+, its
luminescent performance changes as the surrounding con-
ditions change. Lu and Yan41 reported a new ratiometric pH
sensor based on nanoscale PSM MOF-253. Two types of Eu3+
with different excitation wavelengths were simultaneously
present in MOF-253 (Figure 4, top). One of the ions was
insensitive to the pH, and the other one was sensitive to the
pH. In PSM, the Eu3+ ions had two different coordination
environments: Eu1 was linked only to the bipyridine, and Eu2
was linked to both bipyridine and TTA. The broad band at 330
nm was assigned to the excitation of Eu1, and the broad band at
375 nm was mostly from the excitation of Eu2 due to the
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Figure 11. (a, c) Column diagrams of the normalized fluorescence
intensities FMR and FEu toward HI at concentrations of (a) 250 μM
and (c) (0−100 μM). (b, d) Truth tables for (b) the one-to-two
decoder logic gate and (d) the logic analytical device for HI
monitoring. Reproduced with permission from ref 53. Copyright
2017 Wiley-VCH.
energy absorption via TTA. The weakened sensitization caused
the excitation wavelength of Eu2 to be at 375 nm and not 330
nm (Figure 4, bottom). The sensor had a linear response in the
pH range from 5.0 to 7.2, which was required for work with
biological fluids such as blood and cell culture media.
3.3. Cations
Biological iron is most commonly found in the +2 (ferrous)
and +3 (ferric) oxidation states. Luminescence probes to detect
Fe3+ in environmental and biological systems mainly depend on
the quenching effect that metal cations have on the
luminescence of MOFs.42 Xu and Yan36 encapsulated Eu3+
cations into MIL-124 (Ga2(OH)4(C9O6H4)) and used it to
detect Fe3+/Fe2+ ions via the fluorescence quenching of the
dual-emission centers (Eu3+ and the MOF). Although both
Fe2+ and Fe3+ ions significantly quenched the Eu3+ emission,
the emission colors of the two ions were different and easy to
distinguished under UV light. Therefore, Eu3+@MIL-124 could
selectively sense Fe2+ and Fe2+ ions via the different quenching
effects on Eu3+ and the MOF. To detect Fe2+ and Fe3+ in water,
a test paper was immersed in aqueous solutions of the metal
ions, and the fluorescent color changed from red to dark red,
faint dark red, and black with increasing Fe3+ (Figure 5a).
When the test paper was immersed in aqueous solutions with
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Figure 12. Electronic equivalent circuits, truth tables, and column diagrams of the fluorescence intensities of B485, G530 and R614: (a) Hg2+, S2−;
(b) Hg2+, S2−; (c) Ag+, S2−. Reproduced with permission from ref 54. Copyright 2017 Wiley-VCH.

various concentrations of Fe2+, the color changed from red to
blue, as shown in Figure 5b. The quenching effect of Fe3+ on
Eu3+@MIL-124 was ascribed to the partial replacement of Ga3+
by Eu3+, and Eu3+ substitution was the main reason for the
fluorescence quenching due to Fe2+.
Mercury(II) ions are dangerous because of their high toxicity
and carcinogenicity, and qualitative and quantitative detection
of mercury is important. Xu and Yan43 reported encapsulation
of carbon dots (CDs) with strong fluorescence activity into
MOF-253, and the emissions of both the CDs and Eu3+ formed
the dual-emissive Eu3+/CDs@MOF-253. In a solution in the
absence of Hg2+, it exhibited both characteristic emissions of
the CDs and Eu3+ (IEu/ICD = 1.5) with a faint blue light (Figure
6a). In contrast, in the presence of Hg2+ the emission changed
from blue to red under UV light, corresponding to quenching
of the CD emission. Mercury had less of an influence on the
emission of Eu3+ in Eu3+/CDs@MOF-253, which led to a
colorimetric and ratiometric fluorescence Hg2+ sensor. The
quenching effect of Hg2+ on the CDs in Eu3+/CDs@MOF-253
was attributed to the coordination between Hg2+ and functional
G DOI: 10.1021/acs.accounts.7b00387
groups in the CDs. Figure 6b shows the relative photo-
luminescence (PL) intensities (IEu/ICD) versus the concen-
tration of Hg2+. The limit of detection (LOD) was estimated to
be 13 nM, close to the maximum level of mercury in drinking
water permitted by the U.S. Environmental Protection Agency
(2 ppb, 10 nM).
3.4. Anions
As common, toxic anion pollutants, Cr(VI) species (e.g.,
CrO42− and Cr2O72−) are a concern because they cause serious
damage to human health and the environment. Hao and Yan44
investigated the anion recognition of Eu3+@MIL-121 (Al-
(OH)(H2btec)·H2O, H4btec = pyromellitic acid) through Eu3+
coordinated PSM of MIL-121 with its free carboxylate because
its intensity was quenched by most anions. The quenching
effects of F− and Cr2O72− were very pronounced, especially for
Cr2O72− ion. Although both F− and Cr2O72− significantly
quenched the Eu3+ emission, they could be distinguished by
Eu3+@MIL-121. F− ion had a quenching effect only on the Eu3+
luminescence and not the ligand-centered (LC) emission, while
Cr2O72− quenched the emissions of both Eu3+ and the ligand.
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As a result, in the presence of Cr2O72− and F−, the luminescent
color of Eu3+@MIL-121 changed from red to blue and dark,
respectively.
Sun and Yan45 presented a facile, rapid, and selective strategy
for ratiometric sensing of carbonate ions based on hetero-
bimetallic Eu/Pt-MOFs with bpydc as the linker, which had
dual emissions from the ligand and Eu3+. The interaction with
CO32− drastically enhanced the luminescence intensity of Eu3+,
and the maximum ratio of the two intensities (IEu(614)/ILigand)
increased upon the addition of carbonate ions. This might be
an efficient tool for analytical monitoring of trace CO32− in real
samples because of the high orientation selectivity for CO32−.
3.5. Molecules or Solvents
Zhou and Yan46 examined the capability of Eu3+@bpy-UiO
nanohybrids for volatile organic compound (VOC) sensing.
Figure 7a shows the emission spectra of Eu3+@bpy-UiO after
exposure to different VOCs, and the intensity ratio of the
ligand-based emission to the Eu3+ emission (IL/IEu) significantly
depended on the VOC. Moreover, the ratiometric lumines-
cence of Eu3+@bpy-UiO was highly responsive to different
concentrations of VOCs and mixed VOCs. Figure 7b shows the
one-to-one correlation between the resulting IL/IEu and the
encapsulated VOCs. The ratiometric emission intensity and
luminescence quantum yield (Φ) of the VOC-included Eu3+@
bpy-UiO were related to a unique two-dimensional (2D)
readout (IL/IEu, Φ), which was arranged in a decoded map
(Figure 7c). These readouts showed that one can precisely
differentiate the VOCs using this dual-readout process.
Xu and Yan47 prepared a portable luminescent LnMOF film
by in situ growth of nanoscale SUMOF-6-Eu on an oxidation-
treated nonwoven polypropylene surface (NMOFs@O-PP)
(Figure 8). By controlling the excitation wavelength, they
predicted and tuned the emission of the coated NMOFs@O-
PP film with dual-emission bands (IL and IEu). As a result of the
disturbance of the energy transfer from the ligand to Eu3+ in the
NMOFs by O2, the coated NMOFs@O-PP film could be used
for ratiometric O2 sensing. The film showed a high O2
sensitivity (Ksv = 6.73, LOD = 0.45%), short response and
recovery times (10 and 60 s, respectively), and good
reversibility.
3.6. Air Pollutants
Indoor formaldehyde (FA) detection is important for indoor air
pollution (IAP).48−50 Hao and Yan51 fabricated a dual-emissive
Ag+- and Eu3+-functionalized MOF nanohybrid (Ag+/Eu3+@
UiO-66) and utilized it as a self-calibrated ratiometric
luminescent sensor for detection of indoor FA. The two
luminescent centers (centered Eu3+ and ligands) were self-
calibrated. FA interacted with Ag+ and changed the luminescent
behavior of the nanohybrid by weakening the influence of Ag+
ions on the energy transfer process. The IEu/IL data from the
above sensors are shown as bar diagrams in Figure 9a, and the
Ag+-loaded film sensors exhibited excellent selectivity for FA.
The fluorescent responses (IEu/IL) of this sensor to FA in the
presence of various gases were similar to those with only FA
(Figure 9b), which indicated that the effect of FA on the IEu/IL
was not influenced by coexisting gas pollutants.
More recently, Xu and Yan52 fabricated ZnO-doped UiO
MOF heterostructures (ZnO@UiO-MOFs) and turned them
into a dual-emitting material (I614 and I470) by introducing Eu3+
to the UiO-MOFs through coordinated PSM and controlling
the excitation wavelength (Figure 10). Reduced aldehyde
molecules could build a bridge via charge transfer from ZnO to
H DOI: 10.1021/acs.accounts.7b00387
Article
Eu3+ to increase the intensity of I614 and realize selective
sensing. The open connected channels and high surface area of
UiO MOFs could facilitate the effective adsorption of
aldehydes, leading to a low detection limit (42 ppb for FA,
58 ppb for AA, and 66 ppb for ACA). The efficient charge
transfer from the MOFs to ZnO could lead to reusable
detectors for aldehyde gases. In addition, the MOFs showed
stable and reliable fluorescent responses for aldehydes at
different temperatures (25−65 °C), which made them suitable
for practical applications, e.g., vehicle detection.
3.7. Food Spoilage
Unsafe food is a large threat to human health and economies,
and early detection of food spoilage is an ongoing and
imperative need. Sensors (MR@EuMOFs) were created by
covalently attaching methyl red (MR) to NH2-rich EuMOFs. A
double stimuli-responsive fluorescent center was produced via
energy transfers from the ligands to Eu3+ and MR.53 Portable
sensory hydrogels exhibited a color transition upon “smelling”
HI vapor. Using the HI concentration as the input signal and
the two fluorescent emissions as the output signals, an
advanced analytical device based on a one-to-two logic gate
was constructed. The four output combinations NOT (0, 1),
YES (1, 0), PASS 1 (1, 1), and PASS 0 (0, 0) allowed the direct
analysis of HI levels, which could be used for real-time food
freshness evaluations. The normalized fluorescence signals of
MR (FMR) and Eu3+ (FEu) were used as the dual outputs with a
threshold value of 0.5. In the absence of HI, FMR did not
increase and FEu did not decrease, generating the output (0, 1).
After exposure to HI, FMR turned on and FEu turned off,
generating the output (1, 0). Figure 11a,b shows the different
responses of the MR@EuMOFs under various input states. The
output signals were normalized (Figure 11c). In Figure 11d, the
PASS 0 gate was triggered by 40 μM HI, and the YES gate was
triggered by 80 μM HI. When the concentration was below 40
μM, the NOT gates appeared.
3.8. Triple-Luminescent Center for Logic Operations
Xu et al.54 constructed a fluorescent system based on Eu3+-
functionalized UMOFs to effectively combine ion recognition
and logic computing. The Eu3+@UMOFs and ions imple-
mented a Boolean logic network system connecting the
elementary logic operations (NOR, INH, and IMP) and
integrative logic operations (OR + INH). To address uncertain
information in an analogue region with a nonlinear response
(fluorescence and concentration), soft computations via the
formulation of fuzzy logic operations were constructed. On the
basis of Boolean logic and fuzzy logic, an intelligent molecule
search could be realized by using the chemical events (Hg2+,
Ag+, and S2−) as programmable words and the chemical
interactions as the syntax. In the logic operations, Eu3+@
UMOFs served as the gates, and the polluting ions (Hg2+, Ag+,
or S2−) and fluorescent emission changing at 485 nm (B485),
530 nm (G530), and 614 nm (R614) (triple-luminescent
center) were used as the chemical inputs and outputs,
respectively. (Figure 12)
4. CONCLUSIONS AND OUTLOOK
In this Account, recent research progress on lanthanide-
functionalized metal−organic framework (MOF) hybrid
materials is summarized. Lanthanide-ion functionalization of
MOF hosts creates multiple luminescent centers (especially
dual-luminescent centers), and these MOFs can be utilized for
chemical sensing based on the different luminescent responses.
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
Herein, five methods for lanthanide functionalization of MOFs
are outlined according to the interactions between the
lanthanide ions and the MOF host: (1) in situ composition
for MOFs such as ZIF; (2) ionic substitution for lanthanide
MOFs; (3) ionic exchange for anionic MOFs such as Bio-
MOF-1; (4) coordinated postsynthetic modification for MOFs
with free groups in their linkers; and (5) covalent postsynthetic
modification to achieve coordinated groups of MOFs.
Lanthanide functionalization creates multiple luminescent
centers (mainly dual centers) for chemical sensing. Currently,
dual-luminescent-response sensing is being successfully applied
for species in chemistry, biology, and the environment,
including cations, anions, molecules, solvents, and special
biomarkers, as well as pH and temperature. Moreover, the
triple-luminescent response can be used to sense environmental
species, and the logic operation can be further developed.
These luminescent probes can be expected to have potential
applications in chemical sensing for chemical, biological, or
environmental fields, etc. However, some problems still exist in
the field of lanthanide-functionalized MOF hybrids. The
photostability of these hybrid systems needs to be enhanced,
especially in aqueous environments. The fluorescence sensing
mechanism still requires further investigation, and theoretical
calculations on the sensing process are needed. The
disadvantages of fluorescence sensing should be avoided to
improve the low detection limit of this technique compared
with those of other chemical sensing approaches. In addition,
real applications should be explored to prepare practical sensors
to solve problems in complicated systems.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: byan@tongji.edu.cn.
ORCID
Bing Yan: 0000-0002-0216-9454
Notes
The author declares no competing financial interest.
Biography
Bing Yan was born in Changchun, China. He received his Bachelor’s
degree (1992) and Master’s degree (1995) in Applied Chemistry from
Harbin Institute of Technology in China and his Ph.D. (1998) degree
from the Changchun Institute of Applied Chemistry, Chinese
Academy of Sciences, in China. He joined Tongji University as a
full professor in 2001 after his postdoctoral studies at City University
of Hong Kong and Peking University (1998−2001).
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21571142).
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