3d-4f Metal-Organic Framework with Dual Luminescent Centers That Efficiently Discriminates the Isomer and Homologues of Small Organic Molecules

Article abstract of DOI:10.1021/acs.inorgchem.5b02193

A 3d-4f luminescent metal-organic framework (MOF), [Tb₂(Cu₈I₈)(C₁₂H₈NO₂)₆(H₂O)₄]·5C₄H₈O₂ (4), and three analogues {[La₂(Cu₈I₈)(C₁₂H₈NO₂)₆(C₄H₈O₂)₂(H₂O)₂]·3C₄H₈O₂·2H₂O (1), [Ce₂(Cu₈I₈)(C₁₂H₈NO₂)₆(H₂O)₄]·5C₄H₈O₂ (2), and [Eu₂(Cu₈I₈)(C₁₂H₈NO₂)₆(H₂O)₄]·5C₄H₈O₂ (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Φ = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees.

Full text of DOI:10.1021/acs.inorgchem.5b02193

Article
pubs.acs.org/IC
3d−4f Metal−Organic Framework with Dual Luminescent Centers
That Efficiently Discriminates the Isomer and Homologues of Small
Organic Molecules
Guang Zeng, Shanghua Xing, Xiuru Wang, Yulin Yang, Dingxuan Ma, Hongwei Liang, Lu Gao, Jia Hua,
Guanghua Li,* Zhan Shi, and Shouhua Feng
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P.
R. China
S
* Supporting Information
ABSTRACT: A 3d−4f luminescent metal−organic framework
(MOF), [Tb2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (4), and
three analogues {[La2(Cu8I8)(C12H8NO2)6(C4H8O2)2(H2O)2]·
3C4H8O2·2H2O (1), [Ce2(Cu8I8)(C12H8NO2)6(H2O)4]·
5C4H8O2 (2), and [Eu2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2
(3)}, were self-assembled from copper(I) halide clusters and
lanthanide metal ions with an organic linker [3-(pyridin-4-
yl)benzoic acid] under solvothermal conditions. Compound 4
with high quantum yield (Φ = 68%) exhibits reversible
luminescence behavior, accompanying the removal and recovery
of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can
efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it
also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one
another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly
distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the
emissions have shifted, enhanced, weakened, or quenched to different degrees.
improve the detection selectivity and enhance the visible
distinguishability when small organic molecules with similar
chemical and physical properties are probed. Because emission
lights of the dual luminescent centers enhance, weaken, or
quench at different degrees, the MOF sensor would display
various optical signals corresponding to different analytes. To
the best of our knowledge, investigations of MOF sensors with
dual luminescent centers are very limited up to now.6
INTRODUCTION
■
Multinuclear copper(I) halide cluster complexes with d10
electron configurations exhibit intense photoluminescence
properties with potential applications as organic light-emitting
diodes.1 They also respond to exterior stimuli such as thermal
treatment (thermochromism) and mechanical grinding (piezo-
chromism).2 Analysis of the reports on copper(I) halide cluster
complexes in the literature suggests that they are promising
multistimuli-responsive luminescent materials.3
In this work, we aim to design and synthesize a MOF with
dual luminescent centers by using an organic ligand with two
different functional groups [3-(pyridin-4-yl)benzoic acid
(Hpba)] to connect the copper(I) halide cluster and lanthanide
metal ion. Through a study of the hard and soft (Lewis) acid
and base theory, the neutral nitrogen and carboxyl in Hpba are
inclined to connect Cu+ and Ln3+, respectively. Four 3d−4f
luminescent MOFs, [La2(Cu8I8)(pba)6(C4H8O2)2(H2O)2]·
3C4H8O2·2H2O (1), [Ce2(Cu8I8)(pba)6(H2O)4]·5C4H8O2
(2), [Eu2(Cu8I8)(pba)6(H2O)4]·5C4H8O2 (3), and
[Tb2(Cu8I8)(pba)6(H2O)4]·5C4H8O2 (4), are synthesized
under the same solvothermal conditions.
Lanthanide metal−organic frameworks (Ln-MOFs), self-
assembled from lanthanide metal ions with and organic linker,
are a very promising class of luminescent MOF materials.4
Because many Ln-MOFs exhibit sharp and characteristic
emissions, luminescent Ln-MOFs are attractive candidates for
chemical-sensing applications. Up to now, Ln-MOFs have been
extensively studied in sensing ions, vapors, explosives, etc.5
However, most sensors with only one optical signal are usually
based on fluorescence quenching, which lacks sufficient
chemical selectivity and sensitivity. It has been our long-sought
goal to explore a MOF sensor that can clearly differentiate
diverse small organic molecules and provide a unique readout
on the basis of Ln-MOFs. Introducing a second luminescent
center [copper(I) halide clusters] would be a novel strategy to
construct a MOF sensor with high recognition selectivity and
sensing capability. The dual luminescent center may effectively
Received: September 23, 2015
© XXXX American Chemical Society
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EXPERIMENTAL SECTION
■
Materials and Methods. All reagents and solvents used in the
syntheses were obtained from commercial sources without any
purification. Elemental analyses were measured on a PerkinElmer
2400 elemental analyzer. The IR spectra were recorded on a Nicolet
Impact 410 FTIR spectrometer with KBr pellets. Thermogravimetric
analysis (TGA) experiments were carried out by a Q500 V20.10 Build
36 thermogravimetric analyzer from room temperature to 800 °C at a
heating rate of 10 °C min−1. The powder X-ray diffraction (PXRD)
experiments were performed on a Rigaku D/max 2550 powder X-ray
diffractometer with Cu Kα radiation. The quantum yields were
measured with an integrating sphere (C-701, Labsphere Inc.) and a
365 nm Ocean Optics LLS-LED as the excitation source, and the laser
was introduced into the sphere through an optical fiber. The
luminescence spectra were measured on a FluoroMax-4 fluorescence
spectrometer at room temperature. In the chemical-sensing study, all
of the luminescence spectra were recorded in the same test conditions,
and the slit widths of excitation and emission spectra were 2.0 nm.
Synthesis of Compound 4. Tb(NO3)3 (0.045 g, 0.1 mmol), CuI
(19 mg, 0.1 mmol), KI (0.032 g, 0.2 mmol), and 3-(pyridin-4-
yl)benzoic acid (Hpba; 0.030 g, 0.15 mmol) were placed in 5 mL of a
2:3 (v/v) H2O/C4H8O2 (1,4-dioxane) solution, stirred for a few hours,
and then transferred to and sealed in a Teflon-lined steel autoclave.
The autoclave was kept in a 100 °C oven for 5 days. After cooling to
room temperature, light-yellow block crystals were collected by
filtration and washed with 1,4-dioxane (yield 54%). Compounds 1−3
were synthesized in the same conditions. Elem anal. Calcd for
compound 4: C, 31.19; H, 2.73; N, 2.37; O, 11.74. Found: C, 31.66;
H, 2.86; N, 2.23; O, 11.96. Selected IR peak (cm−1): 2961, 2852, 1552,
1400, 1120, 769.
Preparation of Sample 4a. The synthetic samples (4) were
activated under vacuum at 100 °C for 4 h, giving rise to 4a. The TGA
curves and IR spectra of 4a show that the guests have been removed
(Supporting Information, Figures S6 and S7).
Preparation of 4a⊃guest. A total of 5.0 mg of a crystal powder of
4a was immersed in different pure guest solvents (5.0 mL). Then the
samples were treated by ultrasonication and aged for 4 days before
fluorescence testing.
X-ray Crystallography. Single-crystal diffraction data for com-
pound 4 and the analogues were collected on a Rigaku RAXIS-RAPID
diffractometer equipped with a narrow-focus, 5.4 kW sealed-tube X-ray
source (graphite-monochromated Mo Kα radiation with λ = 0.71073
Å). Data processing was accomplished with the PROCESS-AUTO
processing program. Direct methods were used to solve the structure
using the SHELXL crystallographic software package. All non-
hydrogen atoms were easily found from the difference Fourier map.
All non-hydrogen atoms were refined anisotropically. The crystallo-
graphic information and structure refinement details are summarized
in Table S1.
Figure 1. (a) Structure of the Cu8I8 cluster. (b) Structure of the 1D
lanthanide carboxylate chain. (c) 3D structure of the MOFs.
14.3 Å) propagated along the a axis. The channels are occupied
by guest molecules (1,4-dioxane; Supporting Information,
Figure S15).
Photoluminescence Properties. These analogues display
unique photoluminescence properties. The luminescence
spectra of the MOF analogues and Hpba have been measured
in the solid state at room temperature. Among the analogues,
the excitations are around 380 nm (Supporting Information,
Figure S8), and compounds 1 and 2 display a broad emission
band around 615 nm (Figure 2). Because the La3+ and Ce3+
ions are without characteristic emissions and the fluorescence
RESULTS AND DISCUSSION
■
Crystal Structure. X-ray crystal structure analysis reveals
that the four compounds are analogues and they crystallize in
the triclinic P1 space group. In these MOFs, as shown in Figure
̅
1, the Cu8I8 cluster is formed by connecting two Cu4I4 clusters
together through two Cu−I bonds, and the six copper centers
of Cu8I8 bind six nitrogen atoms from six Hpba molecules. The
coordination sphere of the Ln3+ ion is made up of eight oxygen
atoms arising from six carboxylate groups of Hpba and two
terminal water molecules, except that one terminal water
molecule is replaced by 1,4-dioxane in compound 1. The eight-
coordinated Ln3+ ions are further bridged by carboxylate groups
to form an infinite one-dimensional (1D) chain running along
the a axis. Each Cu8I8 cluster is connected with four lanthanide
carboxylate chains through organic linkers to generate an
interesting three-dimensional (3D) framework with two
different sizes of 1D channels (about 7.7 × 9.7 Å and 10.8 ×
Figure 2. Luminescent emission spectra of the four compounds and
desolvated sample 4a.
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of Hpba exhibits one emission maximum at 425 nm, which is
much weaker than the metal-based emission (Supporting
Information, Figure S9), we conclude that the strong and broad
emission band is assigned to the Cu8I8 cluster. Different from
compounds 1 and 2, compounds 3 and 4 provide the
characteristic emission band feature of the Ln3+ ion except
emission from the copper(I) halide cluster (Figure 2). For
compound 3, the characteristic Eu3+ emissions are covered by
the peak of the copper(I) halide cluster. The weak emissions
have been detected at 590, 616, and 698 nm, corresponding
7
7
5
7
5
7
5D0 → F1, D0 → F2, and D0 → F4 to transitions of Eu3+.
For compound 4, the fluorescence peaks at 487, 545, and 620
5
7
5
7
5
nm could be attributed to D4 → F6, D4 → F5, and D4 →
7F3 transitions of the Tb3+ ion.8 Because compound 4 displays
two distinct emission bands from different luminescent centers,
we mainly focus on 4, and its luminescent propertyies will be
studied and discussed in this work.
Sensing of Organic Solvent Molecules. Although there
have been reports of MOF sensors probing different analytes,9
clearly distinguishing small organic molecules and their unique
readouts based on a host MOF sensor is still a challenge,
especially for the isomers. Here we select a desolvated sample
(4a) of compound 4 as the sensor and benzene, toluene, p-
xylene, and mesitylene as the analytes for the chemical-sensing
study. The solvent-free framework 4a is obtained by calcination
of the synthetic samples under vacuum at 100 °C for 4 h, and
the photoluminescence behavior has been measured (Figure 2).
4a displays a broad emission around 687 nm that originated
from the copper(I) halide cluster. Compared to the emission of
4, the broad emission band has weakened and shifted (615 →
687 nm), while the Tb3+ emission bands have almost
disappeared. Moreover, the quantum yields of 68% and 13%
for 4 and 4a, respectively, also confirm that the emission has
greatly weakened. The chemical-sensing study is performed by
soaking 4a crystal powder in selected guest solvents, followed
by luminescence testing. While the powder of 4a is suspended
in each guest liquid (4a⊃guest), the fluorescence spectra are
recorded under excitation at 380 nm, and photographs are
taken after excitation at 365 nm using a commercial ultraviolet
(UV) lamp. The intensity changes and peak shifts are clearly
illustrated in the emission spectra, and the differences can be
distinguished in the images by the naked eye (Figure 3). The
emissions from two luminescent centers have changed to
different degrees, which results in alteration of the optical
signal. In benzene, toluene, and p-xylene solvents, the Tb3+
emissions have obviously been enhanced, while the emissions
that originated from the copper(I) halide cluster have blue-
shifted. However, in the mesitylene solvent, the crystal powder
displays a red emission, which is assigned to the copper(I)
halide cluster, and the Tb3+ emissions have almost disappeared.
In the emission spectra, the enhancing or quenching of
characteristic Tb3+ emissions can be clearly observed. However,
the emission peak of the copper(I) halide cluster has been
covered when the Tb3+ emissions sharply enhance in benzene,
toluene and p-xylene solvents. In order to clearly record how
the emission originating from the copper(I) halide cluster has
changed in different guest solvents, we select compound 2 with
a single emission band as the sensor. The chemical-sensing tests
have been conducted in the same manner as that of 4a by
soaking a desolvated sample (2a) of compound 2 in benzene,
toluene, p-xylene, and mesitylene solvents (Figure 4).
Compared to the emission of 2a, the emissions have a large
blue shift (about 695 → 600 nm) and enhanced in benzene,
Figure 3. Luminescence spectra and photographs of 4a crystal powder
after immersion in different guest solvents: (a) 1,4-dioxane; (b)
benzene; (c) toluene; (d) p-xylene; (e) mesitylene.
Figure 4. Luminescent emission spectra of 2, 2a, and 2a⊃guest
(benzene, toluene, p-xylene, and mesitylene) after excitation at 380
nm.
toluene, and p-xylene solvents. Just like 4a⊃mesitylene,
2a⊃mesitylene displays a red emission that is similar to the
emission of 2a. Especially, 2a⊃guest (toluene and p-xylene)
exhibits another higher-energy (HE) emission band around 490
nm. According to the research results of Ford and co-workers
on copper(I) halide cluster complexes, the HE band should be
attributed to a metal-to-ligand charge-transfer (MLCT) excited
state.10
Sensing Mechanism. The selected guest solvents have
similar chemical and physical properties, but they are of
different sizes. Thus, we speculate that the host should
selectively recognize guest molecules by size. Because the
guest molecules of different sizes would display diverse
arrangement modes in the channel, these would directly affect
interaction of the guest and framework.
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In order to confirm the above speculation, we first analyze
the PXRD patterns of samples 4 and 4a. They are different, and
the first diffraction peak of 4a has shifted to low angle (Figure
5). After 4a is immersed in 1,4-dioxane, the PXRD pattern
is replaced. The PXRD results show that the pattern of the
mesitylene-exchanged sample is nearly the same as the pattern
of sample 4 (Supporting Information, Figure S4), which implies
that the large and small channels are filled with guest molecules.
Considering the size of mesitylene, we speculate that the large
channel would be occupied by mesitylene and the 1,4-dioxane
guests in the small channel would be kept inside. This
speculation has been verified in the fluorescence test results.
The emissions of the mesitylene-exchanged sample are
completely different from that of 4 or 4a⊃mesitylene (Figure
7), indicating that the guests in the channels are not just 1,4-
Figure 5. PXRD patterns of 4 and 4a.
Figure 7. Emission spectra of 4, 4a, 4a⊃mesitylene, and the solvent-
exchanged sample.
dioxane or mesitylene. They should be 1,4-dioxane and
mesitylene, which coexist in the channels. We have also
confirmed speculation by the 1H NMR spectra of the
4a⊃mesitylene and mesitylene-exchanged samples (Supporting
Information, Figures S12−S14).
We have also analyzed the emissions originating from dual
luminescent centers in compound 4. For the center of the
copper(I) halide cluster, the emission is assigned to a triplet-
cluster-centered (3CC) excited state, a combination of halide-
to-metal charge-transfer (XMCT) and d−s transitions.10,11
Because a HE emission band has been detected in the sensing
tests, the MLCT excited state is another important factor that
directly affects the emission of the copper(I) halide cluster. For
the Tb3+ center, because the fluorescence of Hpba is not
observed in the sensing tests, the energy should be effectively
transferred to the lanthanide ion from the organic ligand
(ligand-to-metal energy transfer, LMET).12 The fluorescence
Figure 6. PXRD patterns of 4a after soaking in different guest solvents.
recovers to the initial state (Figure 6). The same results are
obtained in the PXRD test results of the other analogues
(Supporting Information, Figures S1 and S2). These results
illustrate that the framework has changed when 4 transforms
into 4a. Because the available single-crystal data have not been
obtained, it is difficult to directly point out what specific change
has happened. Then, the PXRD patterns of all of the samples
(4a⊃guest) show that the framework has not collapsed and that
most of the patterns are different from the pattern of 4a and
become nearly the same as the pattern of 4. However, the
pattern of 4a⊃mesitylene identifies with the pattern of 4a
(Figure 6). Studying the size of the guests and channel reveals
that all of the guest molecules can enter the large and small
channels except mesitylene, which is too large to enter the small
channel and only enters the large channel. These results
confirm that whether the guests can enter the small channel
largely affects the structure of the framework. Finally, we
further confirm that mesitylene cannot enter the small channel
through a solvent-exchanged experiment. The solvent-
exchanged sample is prepared by immersing the as-synthesized
sample 4 in mesitylene for 3 days to remove the 1,4-dioxane
solvates; the extract is decanted every 4 h, and fresh mesitylene
5
peaks at 487, 545, 584, and 620 nm could be attributed to D4
→ 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3 transitions of the
Tb3+ ion,8 respectively. According to the reported literature, the
structure change would affect the fluorescence of the copper(I)
halide cluster complexes or Ln-MOFs.13 Thus, we speculate
that the sensing mechanism should be attributed to the change
of the structure. This change is likely to directly affect the
ligand and copper(I) halide cluster to different degrees. On the
one hand, the ligand may distort,14 which influences the
LMET13c and MLCT progress.10 On the other hand, the
expansion, contraction, or distortion of the copper(I) halide
cluster would affect the energy of the cluster-centered excited
state.11 When the guest molecules enter into the small and large
channels, the framework is different from the solvent-free
framework and the emission bands completely change. When
the guest molecules only enter the large channels, the
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framework has no obvious difference from the solvent-free
framework and the emissions are nearly the same as the
emission of the desolvated sample. Only the intensities are
different. In addition, the UV−vis absorption spectra of solvent
molecules show that none of them has any observable
absorption intensity around 380 nm (Supporting Information,
Figure S11). Thus, there is no competition between the
absorption of the solvents and the excitation of 4a⊃guest,
which results in quenching.15
Differentiating the Isomers, Homologues, and Chlor-
ides. The recognition selectivity and sensing capability of 4a is
not only manifested by probing the benzene series. As shown in
Figure 8, even the isomers (ether, butyl alcohol, 2-butyl alcohol,
Figure 9. Luminescence spectra of the 4a crystal powder after
immersion in homologues (methanol, ethanol, and n-propanol). Inset:
Luminescence photographs for (a) methanol, (b) ethanol, and (c) n-
propanol.
Figure 10. Luminescence spectra of the 4a crystal powder after
immersion in chloride (CH2Cl2, CHCl3, and CCl4). Inset:
Luminescence photographs for (a) CH2Cl2, (b) CHCl3, and (c) CCl4.
after immersion in guest solvents. An experiment of fast
response is shown in Figure 11; the emission lights completely
Figure 8. Luminescence spectra and photographs of the 4a crystal
powder after immersion in isomers: (a) ether; (b) butyl alcohol; (c) 2-
butyl alcohol; (d) tert-butanol.
and tert-butanol) are unambiguously differentiable. Attributed
to the different sizes of the isomers, ether and butyl alcohol can
enter the small and large channels while 2-butyl alcohol and
tert-butanol can only enter the large channel. Thus, in ether and
butyl alcohol solvents, 4a exhibits Tb3+ emissions at different
intensities while the emission originating from the copper(I)
halide cluster has been covered. When 4a is immersed in 2-
butyl alcohol and tert-butanol, the Tb3+ emissions have almost
disappeared and different intensities of red emissions
originating from the copper(I) halide cluster are shown.
Whether or not the isomers enter the small channel has been
confirmed by the PXRD patterns of 4a⊃guest (ether, butyl
alcohol, 2-butyl alcohol, and tert-butanol; Supporting Informa-
tion, Figure S5). Furthermore, the homologues of butyl alcohol
(methanol, ethanol, and n-propanol) and other small molecules
with similar structural motifs, such as chloride (CH2Cl2, CHCl3,
and CCl4), can also be effectively recognized (Figures 9 and
10).
Figure 11. Luminescence photographs of 4a with fast response to
guest molecules in about 1 s: (a) 4a; (b) one drop of methanol is
added on 4a; (c) one drop of 1,4-dioxane is added on 4a.
change in about 1 s. When one drop of methanol is added on
the desolvated sample of 4a (about 1.0 mg), which is placed on
a glass slide, the emission light immediately turns green. After
the sample dries, one drop of 1,4-dioxane is added onto the
sample, and the emission light changes again in about 1 s. The
whole experiment of fast response has been recorded in a video
(see the Supporting Information).
CONCLUSION
■
In summary, we have successfully prepared a 3d−4f
luminescent MOF that exhibits high recognition selectivity
and sensing capability. Different from the conventional sensor
Fast Response to Organic Solvent Molecules. Apart
from its excellent sensing capability, 4a also has fast response
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L.; Wu, M.; Pan, J.; Wan, X.; Hong, M. J. Mater. Chem. C 2013, 1,
4339−4349.
of Ln-MOF, this MOF contains dual luminescent centers and a
unique porous structure. It effectively differentiates diverse
small organic molecules (benzene series, isomers, homologues,
and chlorides) and provides readouts in corresponding optical
signals. After analysis and discussion, we think that the change
of the structure directly results in luminescence enhancing,
weakening, or quenching. Although the sensing mechanism
needs further investigation, this work demonstrates that the
design of a MOF sensor with dual luminescent centers is an
effective strategy to improve sensing ability.
(4) (a) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T.
Chem. Soc. Rev. 2009, 38, 1330−1352. (b) Rocha, J.; Carlos, L. D.; Paz,
F. A. A.; Ananias, D. Chem. Soc. Rev. 2011, 40, 926−940. (c) Cui, Y.;
Chen, B.; Qian, G. Coord. Chem. Rev. 2014, 273−274, 76−86. (d) Rao,
X.; Song, T.; Gao, J.; Cui, Y.; Yang, Y.; Wu, C.; Chen, B.; Qian, G. J.
Am. Chem. Soc. 2013, 135, 15559−15564. (e) Cui, Y.; Xu, H.; Yue, Y.;
Guo, Z.; Yu, J.; Chen, Z.; Gao, J.; Yang, Y.; Qian, G.; Chen, B. J. Am.
Chem. Soc. 2012, 134, 3979−3982. (f) An, J.; Shade, C. M.; Chengelis-
Czegan, D. A.; Petoud, S.; Rosi, N. L. J. Am. Chem. Soc. 2011, 133,
1220−1223. (g) Tang, Q.; Liu, S.; Liu, Y.; He, D.; Miao, J.; Wang, X.;
Ji, Y.; Zheng, Z. Inorg. Chem. 2014, 53, 289−293. (h) Yang, A.; Zou, J.;
Wang, W.; Shi, X.; Gao, H.; Cui, J.; Zhao, B. Inorg. Chem. 2014, 53,
7092−7100. (i) Wei, Y.; Li, Q.; Sa, R.; Wu, K. Chem. Commun. 2014,
50, 1820−1823. (j) Zhang, Y.; Huang, L.; Miao, H.; Wan, H.; Mei, H.;
Liu, Y.; Xu, Y. Chem. - Eur. J. 2015, 21, 3234−3241.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b02193.
(5) (a) Zhao, B.; Chen, X.; Cheng, P.; Liao, D.; Yan, S.; Jiang, Z. J.
Am. Chem. Soc. 2004, 126, 15394−15395. (b) Lu, W.; Jiang, L.; Feng,
X.; Lu, T. Inorg. Chem. 2009, 48, 6997−6999. (c) Wong, K.; Law, G.;
Yang, Y.; Wong, W. Adv. Mater. 2006, 18, 1051−1054. (d) Zhang, Z.;
Xiang, S.; Rao, X.; Zheng, Q.; Fronczek, F. R.; Qian, G.; Chen, B.
Chem. Commun. 2010, 46, 7205−7207. (e) Guo, Z.; Xu, H.; Su, S.;
Cai, J.; Dang, S.; Xiang, S.; Qian, G.; Zhang, H.; O’Keeffe, M.; Chen,
B. Chem. Commun. 2011, 47, 5551−5553. (f) Guo, Z.; Song, X.; Lei,
H.; Wang, H.; Su, S.; Xu, H.; Qian, G.; Zhang, H.; Chen, B. Chem.
Commun. 2015, 51, 376−379. (g) Song, X.; Song, S.; Zhao, S.; Hao,
Z.; Zhu, M.; Meng, X.; Wu, L.; Zhang, H. Adv. Funct. Mater. 2014, 24,
4034−4041. (h) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012,
112, 1126−1162.
Experimental details, crystal data, IR spectra, XRD
patterns, TGA, luminescence spectra, and UV−vis
1
absorption and H NMR spectra (PDF)
X-ray crystallographic data in CIF format (CIF)
X-ray crystallographic data in CIF format (CIF)
X-ray crystallographic data in CIF format (CIF)
X-ray crystallographic data in CIF format (CIF)
Whole experiment of fast response (ZIP)
AUTHOR INFORMATION
Corresponding Author
*E-mail: leegh@jlu.edu.cn. Phone: +86-431-85168511. Fax:
+86-431-85168624.
■
(6) Dong, M.; Zhao, M.; Ou, S.; Zou, C.; Wu, C. Angew. Chem., Int.
Ed. 2014, 53, 1575−1579.
(7) Chen, B.; Wang, L.; Xiao, Y.; Fronczek, F. R.; Xue, M.; Cui, Y.;
Qian, G. Angew. Chem., Int. Ed. 2009, 48, 500−503.
Notes
(8) Chen, B.; Wang, L.; Zapata, F.; Qian, G.; Lobkovsky, E. B. J. Am.
Chem. Soc. 2008, 130, 6718−6719.
The authors declare no competing financial interest.
(9) (a) Reineke, T. M.; Eddaoudi, M.; Fehr, M.; Kelley, D.; Yaghi, O.
M. J. Am. Chem. Soc. 1999, 121, 1651−1657. (b) Liu, S.; Xiang, Z.; Hu,
Z.; Zheng, X.; Cao, D. J. Mater. Chem. 2011, 21, 6649−6653. (c) Aliev,
S. B.; Samsonenko, D. G.; Rakhmanova, M. I.; Dybtsev, D. N.; Fedin,
V. P. Cryst. Growth Des. 2014, 14, 4355−4363. (d) He, Y.; Zhang, H.;
Liu, Y.; Zhai, Q.; Shen, Q.; Song, S.; Ma, J. Cryst. Growth Des. 2014,
14, 3174−3178. (e) Zhang, M.; Feng, G.; Song, Z.; Zhou, Y.; Chao,
H.; Yuan, D.; Tan, T. T. Y.; Guo, Z.; Hu, Z.; Tang, B.; Liu, B.; Zhao,
D. J. Am. Chem. Soc. 2014, 136, 7241−7244. (f) Pramanik, S.; Zheng,
C.; Zhang, X.; Emge, T. J.; Li, J. J. Am. Chem. Soc. 2011, 133, 4153−
4155. (g) Takashima, Y.; Martínez, V. M.; Furukawa, S.; Kondo, M.;
Shimomura, S.; Uehara, H.; Nakahama, M.; Sugimoto, K.; Kitagawa, S.
Nat. Commun. 2011, 2, 168. (h) Stylianou, K. C.; Heck, R.; Chong, S.
Y.; Bacsa, J.; Jones, J. T. A.; Khimyak, Y. Z.; Bradshaw, D.; Rosseinsky,
M. J. J. Am. Chem. Soc. 2010, 132, 4119−4130. (i) Shustova, N. B.;
ACKNOWLEDGMENTS
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This work was supported by the Foundation of the National
Natural Science Foundation of China (Grants 21371069,
21241010, and 21571077), Specialized Research Fund for the
Doctoral Program of Higher Education (Grant
20110061110015), and National High Technology Research
and Develop Program (863 program) of China (Grant
2013AA031702).
REFERENCES
■
(1) (a) Liu, Z.; Qayyum, M. F.; Wu, C.; Whited, M. T.; Djurovich, P.
I.; Hodgson, K. O.; Hedman, B.; Solomon, E. I.; Thompson, M. E. J.
Am. Chem. Soc. 2011, 133, 3700−3703. (b) Volz, D.; Zink, D. M.;
Bocksrocker, T.; Friedrichs, J.; Nieger, M.; Baumann, T.; Lemmer, U.;
Brase, S. Chem. Mater. 2013, 25, 3414−3426. (c) Zhang, X.; Liu, W.;
Wei, G. Z.; Banerjee, D.; Hu, Z.; Li, J. J. Am. Chem. Soc. 2014, 136,
14230−14236.
(2) (a) Kim, T. H.; Shin, Y. W.; Jung, J. H.; Kim, J. S.; Kim, J. Angew.
Chem., Int. Ed. 2008, 47, 685−688. (b) Braga, D.; Maini, L.; Mazzeo, P.
P.; Ventura, B. Chem. - Eur. J. 2010, 16, 1553−1559. (c) Kitagawa, H.;
Ozawa, Y.; Toriumi, K. Chem. Commun. 2010, 46, 6302−6304.
(d) Perruchas, S.; Goff, X. F. L.; Maron, S.; Maurin, I.; Guillen, F.;
Garcia, A.; Gacoin, T.; Boilot, J. J. Am. Chem. Soc. 2010, 132, 10967−
10969. (e) Zhan, S.; Li, M.; Ng, S. W.; Li, D. Chem. - Eur. J. 2013, 19,
10217−10225. (f) Henline, K. M.; Wang, C.; Pike, R. D. Cryst. Growth
Des. 2014, 14, 1449−1458. (g) Benito, Q.; Le Goff, X. F.; Maron, S.;
Fargues, A.; Garcia, A.; Martineau, C.; Taulelle, F.; Kahlal, S.; Gacoin,
T.; Boilot, J. P.; Perruchas, S. J. Am. Chem. Soc. 2014, 136, 11311−
11320. (h) Li, S.; Zhang, X. Inorg. Chem. 2014, 53, 8376−8383.
(3) (a) Shan, X.; Zhang, H.; Chen, L.; Wu, M.; Jiang, F.; Hong, M.
Cryst. Growth Des. 2013, 13, 1377−1381. (b) Shan, X.; Jiang, F.; Chen,
̆
McCarthy, B. D.; Dinca, M. J. Am. Chem. Soc. 2011, 133, 20126−
20129. (j) Meyer, L. V.; Schonfeld, F.; Muller-Buschbaum, K. Chem.
̈
̈
̈
Commun. 2014, 50, 8093−8108. (k) Hu, Z.; Deibert, B. J.; Li, J. Chem.
Soc. Rev. 2014, 43, 5815−5840. (l) Muller-Buschbaum, K.; Beuerle, F.;
̈
Feldmann, C. Microporous Mesoporous Mater. 2015, 216, 171−199.
(10) (a) Kyle, K. R.; Ryu, C. K.; DiBenedetto, J. A.; Ford, P. C. J. Am.
Chem. Soc. 1991, 113, 2954−2965. (b) Ryu, C. K.; Vitale, M.; Ford, P.
C. Inorg. Chem. 1993, 32, 869−874.
(11) (a) Ford, P. C.; Cariati, E.; Bourassa, J. Chem. Rev. 1999, 99,
3625−3647. (b) Vitale, M.; Ryu, C. K.; Palke, W. E.; Ford, P. C. Inorg.
Chem. 1994, 33, 561−566. (c) Kyle, K. R.; Ford, P. C. J. Am. Chem.
Soc. 1989, 111, 5005−5006. (d) Ford, P. C.; Vogler, A. Acc. Chem. Res.
1993, 26, 220−226. (e) Lee, J. Y.; Kim, H. J.; Jung, J. H.; Sim, W.; Lee,
S. S. J. Am. Chem. Soc. 2008, 130, 13838−13839. (f) Sun, D.; Yuan, S.;
Wang, H.; Lu, H.; Feng, S.; Sun, D. Chem. Commun. 2013, 49, 6152−
6154.
(12) (a) Binnemans, K. Chem. Rev. 2009, 109, 4283−4374.
(b) Eliseeva, S. V.; Bunzli, J. G. Chem. Soc. Rev. 2010, 39, 189−227.
̈
F
DOI: 10.1021/acs.inorgchem.5b02193
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(c) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112, 1126−
1162.
(13) (a) Kim, T. H.; Shin, Y. W.; Jung, J. H.; Kim, J. S.; Kim, J.
Angew. Chem., Int. Ed. 2008, 47, 685−688. (b) Lee, J. Y.; Lee, S. Y.;
Sim, W.; Park, K.; Kim, J.; Lee, S. S. J. J. Am. Chem. Soc. 2008, 130,
6902−6903. (c) Li, Y.; Zhang, S.; Song, D. Angew. Chem. 2013, 125,
738−741.
(14) Zhou, H.; Lin, R.; He, C.; Zhang, Y.; Feng, N.; Wang, Q.; Deng,
F.; Zhang, J.; Chen, X. Nat. Commun. 2013, 4, 3534.
(15) (a) Xiao, Y.; Wang, L.; Cui, Y.; Chen, B.; Zapata, F.; Qian, G. J.
Alloys Compd. 2009, 484, 601−604. (b) Yang, W.; Feng, J.; Song, S.;
Zhang, H. ChemPhysChem 2012, 13, 2734−2738. (c) Hao, Z.; Song,
X.; Zhu, M.; Meng, X.; Zhao, S.; Su, S.; Yang, W.; Song, S.; Zhang, H.
J. Mater. Chem. A 2013, 1, 11043−11050.
G
DOI: 10.1021/acs.inorgchem.5b02193
Inorg. Chem. XXXX, XXX, XXX−XXX