A Three-Dimensional Tetraphenylíethene-Based Metal–Organic Framework for Selective Gas Separation and Luminescence Sensing of Metal Ions

Article abstract of DOI:10.1002/ejic.201600201

A three-dimensional porous metal–organic framework (MOF), UTSA-86, made up of cadmium ions and a chromophoric tetraphenylethene-based tetracarboxylate ligand, 4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(1,1′-biphenyl-4-carboxylic acid (H₄ettc), has been synthesized and characterized by single-crystal X-ray diffraction analysis. This multifunctional MOF exhibits permanent porosity, selective gas uptake, and luminescence sensing of metal ions.

Full text of DOI:10.1002/ejic.201600201

DOI: 10.1002/ejic.201600201
Full Paper
MOFs and Sensors
A Three-Dimensional Tetraphenylethene-Based Metal–Organic
Framework for Selective Gas Separation and Luminescence
Sensing of Metal Ions
[
a]
[a]
[a]
[a]
[b]
Wei Yang, Ganggang Chang, Hailong Wang,* Tong-Liang Hu, Zizhu Yao,
[
c]
[b]
[a,c]
Khalid Alfooty, Shengchang Xiang, and Banglin Chen*
Abstract: A three-dimensional porous metal–organic frame- phenyl-4-carboxylic acid (H ettc), has been synthesized and
4
work (MOF), UTSA-86, made up of cadmium ions and a characterized by single-crystal X-ray diffraction analysis. This
chromophoric tetraphenylethene-based tetracarboxylate li- multifunctional MOF exhibits permanent porosity, selective gas
gand,
4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(1,1′-bi- uptake, and luminescence sensing of metal ions.
Introduction
Given the fact that tetraphenylethene-based cores are very
important functional components for the preparation of func-
[
9]
Metal–organic frameworks (MOFs) or porous coordination poly- tional materials, we chose the tetraphenylethene-based or-
mers (PCPs) are the most brilliant representatives of inorganic– ganic linker 4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(1,1′-
[
1,2]
organic hybrid porous solids.
These new crystalline materials biphenyl-4-carboxylic acid), (H ettc; see Scheme S1 in the Sup-
4
are constructed by the self-assembly of suitable metal ions/clus- porting Information) for assembly with Cd(NO ) ·4H O, which
3
2
2
ters and organic spacers; they therefore possess properties orig- produced the new porous MOF [Cd (ettc) (H O) (dmf)] ·
3
1.5
2
2
n
inating from both inorganic and organic components. Thus far, (dmf)12n (UTSA-86). Single-crystal X-ray diffraction analysis illus-
versatile applications of MOFs and porous CPs have been dis- trated that chains of cadmium are linked by the ettc tetra-
[
3]
[4]
covered, including gas storage and separation, catalysis,
carboxylates in the crystal structure of UTSA-86, generating a
[
5]
[6]
sensing, and electronic devices. New building blocks, that three-dimensional (3D) porous MOF. This new functional MOF,
is, functional organic ligands and metal ions or clusters, have which has both microporous and chromophoric character, ex-
been developed to prepare new MOFs or porous CPs to further hibits moderately high selectivities for CO /CH and CO /N gas
understand and extend their chemistry. In theory it seems separation at room temperature and luminescence sensing of
that an infinite number of MOFs and porous CPs are available the Cu and Zn ions.
by the self-assembly of metal ions/clusters and organic linkers
2
4
2
2
[
7]
2
+
2+
by varying the reaction conditions, and the range of functions
of porous MOFs and CPs no doubt will be greatly extended. Results and Discussion
Nevertheless, the practical demands of these functions have
introduced further challenges, such as thermal/chemical stabil- Crystal Structure of UTSA-86
ity, sensitivity, selectivity, and processability, on the way to real
UTSA-86 was synthesized by the solvothermal reaction between
[
8]
applications that require extensive research endeavors to
comprehend structure–property relationships in detail. Thus, it
is very important to target special MOFs based on functional
organic linkers and metal/clusters.
cadmium nitrate and H ettc in the presence of dmf as solvent
4
at 80 °C. Single-crystal X-ray diffraction analysis revealed that
UTSA-86 crystallizes in the orthorhombic system and belongs
to the Pmna space group. As can be seen in Figure 1 (a,b), there
i
are two kinds of ettc ligands in UTSA-86: One is named ettc
[
a] Department of Chemistry, University of Texas at San Antonio, One UTSA
Circle, San Antonio, Texas 78249-0698, USA
(Figure 1, a) and has four carboxylic groups exhibiting two dif-
1
1
ferent μ -η -η coordination modes (syn-syn and syn-trans
2
E-mail: hailong.wang@utsa.edu
ii
modes) and the other, ettc , has four carboxylic groups showing
μ -η -η -linking modes (Figure 1, b). In addition, there are two
banglin.chen@utsa.edu
2
1
2
http://www.utsa.edu/chem/faculty/BanglinChen.html
b] College of Material Science and Engineering, Fujian Provincial Key
Laboratory of Polymer Materials, Fujian Normal University,
[
[
crystallographically independent, six-coordinate Cd ions with
different coordination environments (Figure 1, c,d). For the Cd1
ion, the coordination sphere is completed by four oxygen at-
oms of ettc ligands, one oxygen atom of a water molecule,
and one oxygen atom of the dmf molecule. The coordination
polyhedron of the Cd2 ion is constructed of two oxygen atoms
3
2 Shangsan Road, Fuzhou 350007, P. R. China
c] Department of Chemistry, Faculty of Science, King Abdulaziz University,
Jeddah 22254, Saudi Arabia
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejic.201600201.
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1
1
of two μ -η -η -coordinated carboxylic groups and four oxygen Powder X-ray Diffraction Pattern and TGA Curve of UTSA-
2
2
1
atoms of two carboxylic groups in the μ -η -η coordination 86
2
mode.
The phase purity of the material in the bulk was confirmed
by elemental analysis and powder X-ray diffraction (PXRD; see
Figure S2). Thermogravimetric analysis (TGA) revealed that the
H2O and dmf molecules of UTSA-86, whether in the guest or
coordinated form, were gradually lost (obsd. 39.2 %, calcd.
8.9 %) in the temperature range of 25 to 205 °C (Figure 3). The
organic spacer of this compound decomposed between 250
and 600 °C, resulting in a residue of CdO (obsd. 15.1 %, calcd.
5.2 %).
3
1
Figure 1. X-ray crystal structure of UTSA-86 showing the coordination confor-
i
ii
mations of a) ettc and b) ettc and the coordination geometries of c) the
Cd1 atom and d) the Cd2 atom (C: black; Cd: purple; N: blue; O: red). All
hydrogen atoms have been omitted for clarity. Symmetry codes, A: 1 – x, y,
z; B: x, 1 – y, z; C: –x, 1 – y, 1 – z; D: –x, y, z; E: –0.5 + x, y, 0.5 + z; F: 1 – x,
Figure 3. TGA curves of UTSA-86 (black line) and the desolvated UTSA-86a
–y, –z; G: x, 1 – y, –z.
(
2
blue line) in the range 25–800 °C under N .
In the crystal structure, the two kinds of Cd ions are bridged
i
by ettc ligands to afford a 3D porous framework (see Figure S1a
in the Supporting Information). The connection between the
Cd ions and ettc linkers yields an infinite 1D ribbon chain (see
Gas Sorption Behavior
ii
To the best of our knowledge, owing to the high coordination
number and large ionic radius of the cadmium ion, it is difficult
to obtain permanently porous MOFs by the self-assembly of
Figure S1b). Integration of the two kinds of Cd ions and ettc
ligands leads to a 3D porous architecture with a very large pore
size (ca. 8.0 × 14.4 Å) along the b axis (Figure 2, a). In contrast,
a microporous structure is observed along the c and a axes
with small pore sizes of around 5.1 and 4.1 Å, respectively (Fig-
[11]
cadmium ions and organic ligands.
The UTSA-86 MOF pos-
sesses very large pores, which encouraged us to examine its
porosity. After the activation of acetone-exchanged crystals of
UTSA-86 under high vacuum at 393 K, a desolvated MOF (UTSA-
3
ure 2, b and Figure S1c). The pore volume of 7023.2 Å of UTSA-
8
6, without taking into consideration any solvent molecules,
8
6a) was produced. The TGA curve of this compound reveals
[
10]
was calculated by using the PLATON
software, and corre-
that the coordinated H O molecules and solvent dmf guests of
2
sponds to a void of around 54 % per unit cell.
UTSA-86 were released completely during the activation proc-
ess, as shown in Figure 3. In addition, the PXRD analysis mani-
fested UTSA-86a to be highly crystalline. The activated UTSA-
8
6a, with an absence of solvent molecules in the pores, exhibits
a slightly different phase to that of the as-synthesized species
see Figure S2 in the Supporting Information); the CO gas sorp-
(
2
tion isotherm at 196 K clearly illustrates its microporous nature
see Figure S3). The Brunauer–Emmett–Teller (BET) surface area
(
2
–1
of UTSA-86a was calculated to be 114 m g , and the pore
volume measured from the CO sorption is 0.11 cm g , which
3
–1
2
is markedly lower than that estimated from the single-crystal
structure. This may be because the host framework is flexible,
and only some pores have been opened by CO molecules.
2
The CO , CH , and N gas sorption isotherms were also meas-
2
4
2
ured at different temperatures to check the porosity and poten-
tial of UTSA-86a for gas separation; the results are shown in
Figure 4. UTSA-86a takes up moderate amounts of carbon diox-
ide (33.0 and 19.2 cm g at 273 and 296 K, respectively),
thereby further confirming the permanent porosity of this acti-
Figure 2. Packings diagram of the X-ray crystal structure of UTSA-86 along
a)the b axis and b) the c axis. The pore surfaces of the channels are high-
lighted as yellow/grey (inner/outer) curved planes (C: black; Cd1: purple; Cd2:
blue; O: red). All solvent moelculea have been omitted for clarity,.
3
–1
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vated MOF. The coverage-dependent adsorption enthalpy of to model the typical composition of flue gas mixtures from
UTSA-86a with respect to the CO molecule was calculated by power plants, the calculated selectivities for CO /N (15:85)
2
2
2
using the virial method to improve the understanding of CO2 span the range of 24.6–35.1 at 296 K, which indicates the po-
sorption behavior (see Figure S4 in the Supporting Information). tential of UTSA-86a as a promising adsorbent in the real process
The enthalpy of adsorption at zero coverage of UTSA-86a is of CO /N separation.
2
2
–
1
2
5.0 kJ mol for CO , which is even comparable with some
2
–1 [12]
MOFs with open metal sites, such as HKUST-1 (26 kJ mol )
–1 [12]
and PCN-11 (23 kJ mol ). Compared with the uptake of CO2,
UTSA-86a adsorbs smaller amounts of methane (7.9 and
3
–1
3
–1
4
2
.9 cm g ) and nitrogen (5.1 and 1.8 cm g ) at 273 and
96 K, respectively, and 1 atm, and the enthalpies at zero cover-
age of UTSA-86a are 14.4 and 10.1 kJ/mol for CH and N , re-
4
2
spectively. The clearly different gas uptakes and enthalpies for
CO , CH , or N confirm the different affinities of UTSA-86a for
2
4
2
these gas substrates, which shows the potential capacity of this
new MOF for the selective separation of CO /N and CO /CH .
2
2
2
4
Figure 5. Mixture adsorption isotherms and adsorption selectivities of UTSA-
6a for CO /CH (50:50) and CO /CH (15:85) at a–c) 273 K and d) 296 K as
predicted by IAST.
8
2
4
2
4
Luminescence Sensing of Different Metals
The combination of TPE-based ligands and suitable metal ions,
1
0
such as d ions, is a good strategy for constructing photolumi-
nescent materials. The luminescent properties of TPE-based
MOFs are very interesting because of their very high quantum
yields and thus various applications in light-emitting devices
Figure 4. CO
2 4 2
(red), CH (blue), and N (black) sorption isotherms of UTSA-86a
[
22,23]
and chemical sensors.
As a consequence, we studied the
at a) 273 and b) 296 K (solid symbols: adsorption; open symbols: desorption).
luminescent properties of H ettc and the complex UTSA-86 in
4
the solid state at room temperature. The luminescence spec-
Gas separation is of particular interest when exploring the trum of the free H ettc ligand displays an emission maximum
4
functionalities of MOFs as they are very useful for obtaining at 522 nm (λex = 350 nm). This is typical of intraligand transi-
[
24a]
highly pure gases in industry. We have therefore also been very tions, based on previous reports in the literature.
After the
interested in the use of porous MOF materials for gas separa- self-assembly of Cd and the H TTC ligand, a clear blueshift of
4
[
13–16]
tion.
Currently, it is very popular to deduce the selectivity the emission is observed, with a maximum at 472 nm (λex =
of MOFs towards binary gas mixtures by utilizing the well- 350 nm) in the luminescence spectrum of UTSA-86 (see Fig-
[
17]
known ideal adsorbed solution theory (IAST) calculation with ure S7 in the Supporting Information), which is associated with
[
18]
[24]
the help of the dual-site Langmuir–Freundlich (DSLF) model.
By using the IAST method, we calculated the adsorption iso- ally observed for tetraphenylethene-based MOFs.
therms and selectivities for CO /CH (50:50) and CO /N (15:85) be noted that the intraligand luminescence of TPE-based li-
an aggregate-induced effect (AIE).
This phenomenon is usu-
[
25]
It should
2
4
2
2
at different pressures and temperatures. The pressure-inde- gands is very sensitive to molecular conformation, aggregation
[
26]
pendent mixed-gas isotherms and selectivities for this activated state, and the coordinated metal species. In addition, turn-on
MOF are shown in Figure 5 and Figures S5 and S6 in the Sup- luminescence is often observed in TPE-based sensors.[ These
porting Information. The gas selectivities were determined to characteristics enable TPE-based MOFs to sensitively distinguish
be 11.3 and 7.1 for CO /CH and 17.8 and 24.2 for CO /N at different chemicals and thus be very good candidates for chem-
25]
2
4
2
2
2
73 and 296 K, respectively. Selective CO uptake is very useful ical sensing. After the immersion of UTSA-86 crystals in dmf
2
+
+
2+
2+
for the purification of natural and flue gases. The selectivity for solutions containing M(NO ) ·nH O (M = Na , Ag , Cu , Mg ,
3
2+
x
2
2
+
2+
2+
2+
3+
CO /CH separation by adsorption is 11.3 at 273 K, which is Zn , Mn , Co , Ni , Ca , and Cr ) at a concentration of
2
4
comparable to the high values reported for other microporous 1.0 × 10–
2
M
, the luminescence of the treated UTSA-86 was
MOF materials under similar conditions, including Tb(BCB) (ca. measured to investigate the potential of UTSA-86 for the lumi-
[
19]
[20]
[21]
4
.1), La(BTB) (ca. 6.4), and InOF-14 (ca. 3.1). In addition, nescence sensing of different metals.
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The various metal ions clearly show different influences on the Cd ion is usually greater than six.[27] As a consequence,
[
27]
the luminescence of UTSA-86 (Figure 6). With zinc nitrate, the cadmium may be easily replaced by other transition metals.
emission of the treated UTSA-86 exhibits a redshifted (15 nm) The differences observed in the luminescence may be due to
emission with a maximum at 487 nm and an enhanced intensity ion exchange. As expected, a clear color change between the
compared with the original crystals. In contrast, no significant original UTSA-86 (slightly yellow) and the species immersed in
2
+
–2
spectral shifts were observed for UTSA-86 treated with other Cu solution (1.0 × 10
M; green) is observed (see Figure S9),
metal nitrate solutions. However, all the paramagnetic metals which confirms that Cu ions are incorporated into the UTSA-
2
+
2+
2+
2+
3+
(
Cu , Mn , Co , Ni , and Cr ) induced a decrease in the 86. Energy-dispersive X-ray (EDX) analysis further confirmed the
2
+
luminescence intensity at 472 nm. In the presence of Cu , 98 % presence of Cu ions within UTSA-86 (see Figures S10 and S11),
of the luminescence intensity of UTSA-86 was quenched. The and the replacement of around 50 % of the Cd ions by Cu
diamagnetic metals Na and Mg caused an enhanced and ions was determined by elemental analysis. This quenching ef-
unchanged intensity of the processed UTSA-86, respectively, fect of Cu is a normal phenomenon for MOF sensors. The
2
+
2+
+
2+
2
+
2
+
+
2+
9
whereas both Ca and Ag caused a decrease in the emission Cu ion has an unsaturated d electron configuration with the
2
+
intensity. It should be noted that samples treated with Zn and low-lying electron levels made up of partially filled d orbitals.
+
Na ions in dmf solution show turn-on luminescence phenom- The d–d transitions between these levels are non-emissive and
ena with a shift in the emission wavelength and an enhance- lead to strong re-absorption, which usually weakens or
[
5a]
ment in the luminescence intensity, respectively. The lumines- quenches the MOF luminescence.
This is also true for the
cence intensity at 472 nm of the latter sample is only moder- luminescence of samples treated with solutions of paramag-
ately enhanced (19 %), which is not sensitive enough to be dis- netic ions. In contrast, the different emission intensities and
tinguished by the naked eye. These results indicate that UTSA- shifts in emission wavelengths of the sample after immersion
6 is able to selectively distinguish Zn2 and Cu ions from in different diamagnetic metal solutions may be caused by the
+
2+
8
other metal ions based on the clear turn-on and quenching different intra- and/or intermolecular energy transfer in the ettc
luminescence phenomena, respectively. To comprehend the ligand(s). However, the specific mechanism is still not clear.
sensing mechanism, we performed powder X-ray diffraction
measurements on UTSA-86 samples treated with different metal
–
2
Conclusions
ions (10
treated samples match well that of the as-synthesized UTSA-86
see Figure S8 in the Supporting Information), which indicates
M) in dmf solution for 36 h. The PXRD patterns of the
We have successfully prepared a new multifunctional metal–
organic framework, UTSA-86. The activated species shows per-
manent porosity and moderately high selectivities for mixed
CO /CH and CO /N gas separations, as predicted by IAST cal-
(
that the structure of the framework is maintained. Furthermore,
we investigated the crystal structure again. The Cd ions are lo-
cated in different six-coordinate environments; such coordina-
tion polyhedrons are not stable as the coordination number of
2
4
2
2
culations. In addition, the MOF has potential applications in the
chemical sensing of divalent Zn and Cu ions by means of the
luminescence turn-on and quenching effect. We are now ex-
ploring the use of new functional carboxylic acids to synthesize
further MOFs with multiple functions.
Experimental Section
General: All reagents and solvents were used as received from com-
mercial suppliers without further purification. Tetrakis(4-bromo-
[
28]
phenyl)ethene was prepared according to the literature.
Tetra-
methyl-4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(1,1′-biphen-
yl-4-carboxylate) (Me ettc) and 4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tet-
4
rayl)tetrakis(1,1′-biphenyl-4-carboxylic acid) (H ettc) were prepared
4
according to slight modifications of the reported procedures (see
[
29]
Scheme S1 in the Supporting Information).
NMR spectra were
recorded with a Varian INOVA 500 MHz spectrometer at room tem-
perature. CDCl (δ = 7.26 ppm) and [D ]DMSO (δ = 2.50 ppm) were
3
6
1
used as internal standards for the H NMR spectra. The FTIR spec-
trum was recorded with a Bruker Vector 22 IR spectrometer at room
temperature. Thermogravimetric analysis (TGA) was performed with
a Shimadzu TGA-50 thermogravimetric analyzer under N at a heat-
2
ing rate of 3 °C/min. Elemental analysis was performed with a Per-
kin–Elmer 240 CHN analyzer from Galbraith Laboratories. Steady-
state fluorescence spectroscopic studies were performed with an
Hitachi F 4500 instrument using a slit width of 5.0 nm for excitation
and 2.5 nm for emission. The photomultiplier voltage was 700 V.
Scanning electron microscope (SEM) was performed with a SIRION-
100 instrument on a powder sample previously dried and sputter-
Figure 6. a) Emission spectra and b) photoluminescence intensities for com-
plex UTSA-86 and samples of UTSA-86 treated with different metal ions
–2
(
10
M) in dmf solution at room temperature for 36 h.
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coated with a thin layer of gold. Energy-dispersive X-ray spectro-
Cu2+, Mg2+, Zn2+, Mn2+, Co2+, Ni2+, Ca2+, and Cr3+). After immersion
for 36 h, the treated crystals were filtered and their solid lumines-
cence determined.
II
scopy (EDX) analysis was performed to confirm the presence of Cu
II
II
and the replacement of Cd by Cu .
Cd (ettc) (H O) (dmf)] ·(dmf) (UTSA-86): The starting mate-
12n
[
3
1.5
2
2
n
rials Cd(NO ) ·4H O (0.15 g), H ettc (0.08 g), and dmf (5 mL) were
sealed in a 23 mL vial, which was heated at 80 °C for 48 h. After
being cooled to room temperature, the vial was cut open; slightly
3
2
2
4
Acknowledgments
This work was supported by the Welch Foundation (grant num-
yellow crystals suitable for X-ray diffraction were obtained by filtra- ber AX-1730, grant to B. C.).
tion in a yield of 0.11 g, 43 % (based on H ettc ligand). IR (KBr): ν =
4
˜
3
(
031 (m), 1641 (m), 1574 (m), 1514 (s), 1374 (s), 985 (s), 823 (s), 760
m) cm . C120H143Cd N O : C 56.82, H 5.68, N 7.18; found C 56.78,
Keywords: Metal–organic frameworks · Microporous
materials · Gas separation · Luminescence · Sensors · Ligand
design
–1
3 13 27
H 5.63, N 7.17.
Single-Crystal X-ray Diffraction: Crystallographic data for a single
crystal of UTSA-86 was collected with an Oxford Diffraction Super-
Nova diffractometer with Cu-Kα radiation (λ = 1.54184 Å) at
[1] a) H. Furukawa, K. E. Cordova, M. O'Keeffe, O. M. Yaghi, Science 2013,
341, 974; b) J.-P. Zhang, Y.-B. Zhang, J.-B. Lin, X.-M. Chen, Chem. Rev.
1
00.00(16) K. The final unit cell parameters were derived from
2012, 112, 1001–1033; c) O. K. Farha, J. T. Hupp, Acc. Chem. Res. 2010,
global refinements of reflections obtained from the integration of
4
3, 1166–1175; d) M. Li, D. Li, M. O'Keeffe, O. M. Yaghi, Chem. Rev. 2014,
all frame data. The collected frames were integrated by using the
preliminary cell-orientation matrix. CrysAlisPro[
30]
114, 1343–1370; e) Y. Cui, B. Li, H. He, W. Zhou, B. Chen, G. Qian, Acc.
Chem. Res. 2016, 49, 483–493.
software was
used to collect the frames of data, index the reflections, and deter-
mine the lattice constants. SCALE3 ABSPACK software[ was util-
ized for absorption correction. The structure was solved by direct
[
2] a) J. E. Mondloch, M. J. Katz, W. C. Isley III, P. Ghosh, P. Liao, W. Bury, G. W.
Wagner, M. G. Hall, J. B. DeCoste, G. W. Peterson, R. Q. Snurr, C. J. Cramer,
J. T. Hupp, O. K. Farha, Nat. Mater. 2015, 14, 512–516; b) Z. Zhang, H. T. H.
Nguyen, S. A. Miller, S. M. Cohen, Angew. Chem. Int. Ed. 2015, 54, 6152–
6157; Angew. Chem. 2015, 127, 6250; c) H. Wu, Y. S. Chua, V. Krunglevici-
ute, M. Tyagi, P. Chen, T. Yildirim, W. Zhou, J. Am. Chem. Soc. 2013, 135,
30]
methods (SHELXS-97) and refined by full-matrix least-squares meth-
ods on F2 (SHELXL-97).
[31]
Anisotropic thermal parameters were
used for the non-hydrogen atoms and isotropic parameters for the
hydrogen atoms. Hydrogen atoms were added geometrically and
refined by using a riding model. The “PART” restraint was used to
deal with the disorder of the benzene ring in the ettc ligand. In
addition, we note that the “SQUEEZE” command was employed be-
cause of the seriously disordered solvent molecules in the UTSA-86
pores. Selected crystallographic data and pertinent information for
this compound are summarized in Table S1, and selected bond
lengths and angles are listed in Table S2.
1
0525; d) Q.-L. Zhu, Q. Xu, Chem. Soc. Rev. 2014, 43, 5468–5512.
[
3] a) J.-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869–932; b) H. Wu,
Q. Gong, D. H. Olson, J. Li, Chem. Rev. 2012, 112, 836–868; c) H. Sato, W.
Kosaka, R. Matsuda, A. Hori, Y. Hijikata, R. V. Belosludov, S. Sakaki, M.
Takata, S. Kitagawa, Science 2014, 343, 167–170; d) R. Vaidhyanathan,
S. S. Iremonger, G. K. H. Shimizu, P. G. Boyd, S. Alavi, T. K. Woo, Science
2010, 330, 650–653; e) C. Serre, C. Mellot-Draznieks, S. Surblé, N. Aude-
brand, Y. Filinchuk, G. Férey, Science 2007, 315, 1828–1831; f) P. Nugent,
Y. Belmabkhout, S. D. Burd, A. J. Cairns, R. Luebke, K. Forrest, T. Pham, S.
Ma, B. Space, L. Wojtas, M. Eddaoudi, M. J. Zaworotko, Nature 2013, 495,
CCDC 1455687 (for UTSA-86) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
8
0–84; g) K. A. Cychosz, A. G. Wong-Foy, A. J. Matzger, J. Am. Chem. Soc.
2
2
009, 131, 14538–14543; h) B. Chen, S. Xiang, G. Qian, Acc. Chem. Res.
010, 43, 1115–11124; i) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDo-
nald, E. D. Bloch, Z. R. Herm, T.-H. Bae, J. R. Long, Chem. Rev. 2012, 112,
24–781.
4] a) T. Zhang, W. Lin, Chem. Soc. Rev. 2014, 43, 5982–5993; b) J. Liu, L.
Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011–
Gas Sorption Measurements: Before the gas sorption measure-
ments, as-synthesized crystals of UTSA-86 were exchanged with dry
acetone six times and then evacuated at 6 μmmHg at 393 K to
generate activated UTSA-86. Gas sorption data of activated UTSA-
7
[
6
5
061; c) W.-Y. Gao, M. Chrzanowski, S. Ma, Chem. Soc. Rev. 2014, 43,
841–5866; d) M. Zhao, S. Ou, C.-D. Wu, Acc. Chem. Res. 2014, 47, 1199–
8
6 were collected by using a Micromeritics ASAP 2020 surface area
analyzer; the measurement temperatures were maintained at 196,
73, and 296 K by using a bath of dry ice/acetone slurry, an ice/
1207.
2
[5] a) Y. Cui, Y. Yue, G. Qian, B. Chen, Chem. Rev. 2012, 112, 1126–1162; b)
L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. V. Duyne, J. T. Hupp,
Chem. Rev. 2012, 112, 1105–1125; c) Z. Hu, B. J. Deibert, J. Li, Chem. Soc.
Rev. 2014, 43, 5815–5840.
[6] a) J. Yu, Y. Cui, H. Xu, Y. Yang, Z. Wang, B. Chen, G. Qian, Nat. Commun.
2013, 4, 2719; b) P. Ramaswamy, N. E. Wong, G. K. H. Shimizu, Chem. Soc.
Rev. 2014, 43, 5913–5932; c) V. Stavila, A. A. Talin, M. D. Allendorf, Chem.
Soc. Rev. 2014, 43, 5994–6010; d) L. Sun, T. Miyakai, S. Seki, M. Dincă, J.
Am. Chem. Soc. 2013, 135, 8185–8188.
7] a) M. Eddaoudi, D. F. Sava, J. F. Eubank, K. Adil, V. Guillerm, Chem. Soc.
Rev. 2015, 44, 228–249; b) Y. He, B. Li, M. O'Keeffe, B. Chen, Chem. Soc.
Rev. 2014, 43, 5618–5656; c) W. Lu, Z. Wei, Z.-Y. Gu, T.-F. Liu, J. Park, J.
Tian, M. Zhang, Q. Zhang, T. Gentle III, M. Bosch, H.-C. Zhou, Chem. Soc.
Rev. 2014, 43, 5561–5593.
water mixture, and a water bath in an air-conditioned 23 °C labora-
tory, respectively.
IAST Calculations: The adsorption isotherms and gas selectivities
of CO /CH (50:50) and CO /N (15:85) at 273 and 296 K were calcu-
2
4
2
2
lated based on the ideal adsorbed solution theory (IAST) proposed
by Myers and Prausnitz,[
17]
The results are shown in Figure 5, Fig-
ures S5 and S6, and Table S3 in the Supporting Information. To
weight the sorption performance of this MOF towards the separa-
tion of binary mixed gases, the parameters fitted from the single-
component CO , CH , and N adsorption isotherms based on the
[
2
4
2
dual-site Langmuir–Freundlich (DSLF) model were used in the IAST
calculations.[ The fitting parameters of the DSLF equation are
listed in Table S4.
18]
[8] a) A. G. Slater, A. I. Cooper, Science 2015, 348, aaa8075; b) N. C. Burtch,
H. Jasuja, K. S. Walton, Chem. Rev. 2014, 114, 10575–10612.
[
9] R. Hu, N. L. C. Leung, B.-Z. Tang, Chem. Soc. Rev. 2014, 43, 4494–4562.
Luminescence Sensing of UTSA-86: The luminescence of UTSA-86
was investigated in the solid state at room temperature and com-
[
10] A. L. Spek, PLATON, A Multipurpose Crystallographic Tool, Utrecht Univer-
sity, The Netherlands, 2005.
[11] a) H.-R. Fu, F. Wang, J. Zhang, Dalton Trans. 2014, 43, 4668–4673; b) Y.
Chen, Z. Li, Q. Liu, Y. Shen, X. Wu, D. Xu, X. Ma, L. Wang, Q.-H. Chen, Z.
Zhang, S. Xiang, Cryst. Growth Des. 2015, 15, 3847–3852; c) H. He, Y.
pared with that of H ettc. For the experiments involving the sensing
4
metal ions, crystals of UTSA-86 (15 mg) were immersed in dmf solu-
–
2
+
+
tions (20 mL) containing 1 × 10
M
of M(NO ) ·nH O (M = Na , Ag ,
3 x 2
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5
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Full Paper
Song, C. Zhang, F. Sun, R. Yuan, Z. Bian, L. Gao, G. Zhu, Chem. Commun.
015, 51, 9463–9466.
12] J. M. Simmons, H. Wu, W. Zhou, T. Yildirim, Energy Environ. Sci. 2011, 4,
177–2185.
13] a) T. Hu, H. Wang, B. Li, R. Krishna, H. Wu, W. Zhou, Y. Zhao, Y. Han, X.
Wang, W. Zhu, Z. Yao, S. Xiang, B. Chen, Nature Commun. 2015, 6, 7328;
b) Y. Yue, J. Rabone, H. Liu, S. Mahurin, M. Li, H. Wang, Z. Lu, B. Chen, J.
Wang, Y. Fang, S. Dai, J. Phys. Chem. C 2015, 119, 9442–9449; c) J. Yu, Y.
Cui, C. Wu, Y. Yang, B. Chen, G. Qian, J. Am. Chem. Soc. 2015, 137, 4026.
14] a) W. Yang, B. Li, H. Wang, O. Alduhaish, K. Alfooty, M. Zayed, P. Li, H.
Arman, B. Chen, Cryst. Growth Des. 2015, 15, 2000–2004; b) P. Li, Y. He,
Y. Zhao, L. Weng, H. Wang, R. Krishna, H. Wu, W. Zhou, M. O'Keeffe, Y.
Han, B. Chen, Angew. Chem. Int. Ed. 2015, 54, 574–577; Angew. Chem.
b) Z. Hu, G. Huang, W. P. Lustig, F. Wang, H. Wang, S. J. Teat, D. Banerjee,
D. Zhang, J. Li, Chem. Commun. 2015, 51, 3045–3048.
2
[
[
[23] a) N. B. Shustova, A. F. Cozzolino, S. Reineke, M. Baldo, M. Dincă, J. Am.
Chem. Soc. 2013, 135, 13326–13329; b) Z. Hu, W. P. Lustig, J. Zhang, C.
Zheng, H. Wang, S. J. Teat, Q. Gong, N. D. Rudd, J. Li, J. Am. Chem. Soc.
2015, 137, 16209–16215; c) M. Zhang, G. Feng, Z. Song, Y.-P. Zhou, H.-Y.
Chao, D. Yuan, T. T. Y. Tan, Z. Guo, Z. Hu, B.-Z. Tang, B. Liu, D. Zhao, J.
Am. Chem. Soc. 2014, 136, 7241–7244.
[24] a) Z. Wei, Z.-Y. Gu, R. K. Arvapally, Y.-P. Chen, R. N. McDougald Jr., J. F. Ivy,
A. A. Yakovenko, D. Feng, M. A. Omary, H.-C. Zhou, J. Am. Chem. Soc.
2014, 136, 8269–8276; b) X. Wang, J. Hu, G. Zhang, S. Liu, J. Am. Chem.
Soc. 2014, 136, 9890–9893.
2
[
[25] a) N. B. Shustova, B. D. McCarthy, M. Dincă, J. Am. Chem. Soc. 2011, 133,
20126–20129; b) N. B. Shustova, T.-C. Ong, A. F. Cozzolino, V. K. Michaelis,
R. G. Griffin, M. Dincă, J. Am. Chem. Soc. 2012, 134, 15061–15070.
2015, 127, 584; c) Z. Guo, D. Yan, H. Wang, D. Tesfagaber, X. Li, Y. Chen,
W. Huang, B. Chen, Inorg. Chem. 2015, 54, 200–204.
15] a) Y. Cui, F. Zhu, B. Chen, G. Qian, Chem. Commun. 2015, 51, 7420–7431;
b) P. Li, H. Arman, H. Wang, L. Weng, K. Alfooty, R. F. Angawi, B. Chen,
Cryst. Growth Des. 2015, 15, 1871–1875.
16] a) H. Alawisi, B. Li, K. Alfooty, L. Wu, S. Xiang, H. Wang, B. Chen, Inorg.
Chem. Commun. 2014, 106–109; b) D. Yan, B. Chen, Q. Duan, Inorg. Chem.
Commun. 2014, 34–36.
[
[
[
26] a) J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam, B.-Z. Tang, Chem. Rev.
015, 115, 11718–11940; b) J. Wang, J. Mei, R. Hu, J.-Z. Sun, A. Qin, B.-Z.
2
Tang, J. Am. Chem. Soc. 2012, 134, 9956–9966.
[
27] a) Z. Zhang, L. Wojtas, M. Eddaoudi, M. J. Zaworotko, J. Am. Chem. Soc.
2013, 135, 5982–5985; b) Z. Zhang, L. Zhang, L. Wojtas, P. Nugent, M.
Eddaoudi, M. J. Zaworotko, J. Am. Chem. Soc. 2012, 134, 924–927.
28] H. Wang, B. Li, H. Wu, T.-L. Hu, Z. Yao, W. Zhou, S. Xiang, B. Chen, J. Am.
Chem. Soc. 2015, 137, 9963–9970.
[
[
17] A. L. Myers, J. M. Prausnitz, AIChE J. 1965, 11, 121–127.
18] D. Banerjee, Z. Zhang, A. Plonka, J. Li, J. Parise, Cryst. Growth Des. 2012,
[
[
[
[
1
2, 2162–2165.
29] Q. Zhang, J. Su, D. Feng, Z. Wei, X. Zou, H.-C. Zhou, J. Am. Chem. Soc.
[
[
[
[
19] Z. Guo, X. Song, H. Lei, H. Wang, S. Su, H. Xu, G. Qian, H. Zhang, B. Chen,
Chem. Commun. 2015, 376–379.
20] Z.-J. Lin, Y.-B. Huang, T.-F. Liu, X.-Y. Li, R. Cao, Inorg. Chem. 2013, 52, 3127–
2
015, 137, 10064–10067.
30] CrysAlisPro, version 1.171.33.66, Oxford Diffraction Ltd., Abingdon, U. K.,
010.
31] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
2
3132.
21] J. Qian, Q. Li, L. Liang, Y. Yang, Z. Cao, P. Yu, S. Huang, M. Hong, Chem.
Commun. 2016, DOI: 10.1039/c5cc10359b.
22] a) Q. Gong, Z. Hu, B. J. Deibert, T. J. Emge, S. J. Teat, D. Banerjee, B.
Received: February 27, 2016
Mussman, N. D. Rudd, J. Li, J. Am. Chem. Soc. 2014, 136, 16724–16727;
Published Online: ■
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Full Paper
MOFs and Sensors
A three-dimensional multifunctional
metal–organic
framework
(MOF),
W. Yang, G. Chang, H. Wang,*
T.-L. Hu, Z. Yao, K. Alfooty,
S. Xiang, B. Chen* .............................. 1–7
UTSA-86, made up of cadmium ions
and a tetraphenylethene-based tetra-
carboxylate ligand has been synthe-
sized and characterized by single-crys-
tal X-ray diffraction analysis. This MOF
exhibits permanent porosity, selective
gas uptake, and luminescence sensing
of metal ions.
A Three-Dimensional Tetraphenyl-
ethene-Based Metal–Organic Frame-
work for Selective Gas Separation
and Luminescence Sensing of Metal
Ions
DOI: 10.1002/ejic.201600201
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7
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim