A 3D MOF showing unprecedented solvent-induced single-crystal-to-single-crystal transformation and excellent CO2 adsorption selectivity at room temperature

Article abstract of DOI:10.1039/c4cc06588c

A water stable porous 3D metal-organic framework, [Cu₃L₂(μ₃-OH)₂(μ₂-H₂O)]·2DMA (1, mother crystal, H₂L = 2,2′-dinitrobiphenyl-4,4′-dicarboxylic acid, DMA = N,N-dimethylacetamide), shows unprecedented irreversible solvent-induced substitutions of bridging aqua ligands and guest-exchanges in single-crystal-to-single-crystal (SCSC) transformations at room temperature (RT), producing quantitatively three daughter crystals, [Cu₃L₂(μ₃-OH)₂]·2S (2: 2A, S = acetone; 2B, S = 2-propanol; 2C, S = 2-butanol), which exhibit reversible interconversion by guest-exchanges at RT in SCSC transformations. MOF 1 shows excellent separation selectivity (128) of CO₂/N₂ at RT and is a better sorbent of micro-solid-phase extraction (μ-SPE) than currently known benchmark ZIF-8.

Full text of DOI:10.1039/c4cc06588c

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A 3D MOF showing unprecedented solvent-induced
single-crystal-to-single-crystal transformation and
excellent CO2 adsorption selectivity at room
temperature
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
Tao Qin,‡a Jun Gong,‡a Junhan Ma,a Xin Wang,a Yonghua Wang,b Yan Xu,a Xuan
Shena and Dunru Zhu∗a
DOI: 10.1039/x0xx00000x
www.rsc.org/
bond formation at RT in a 2D MOF.10e In 3D MOFs, however, no
example has been reported.
A
water stable porous 3D metal-organic framework,
[Cu3L2(
ꢀ
3-OH)2(
ꢀ
2-H2O)]·2DMA (1, mother crystal, H2L =
N,N
As a new generation of porous materials, MOFs possess high
surface areas, large internal pore volumes and tunable pore sizes.
However, many MOFs built from multicarboxylateꢀbridging ligands
are prone to decomposition upon exposure to atmospheric water,11a
greatly limiting their industrial or commercial applications.
Therefore, the design and exploitation of water stable MOFs are
quite crucial for practical applications as functional materials.11b To
date, only few carboxylateꢀbased porous MOFs materials have
shown good stabilities toward water.12 Moreover, the design and
fabrication of porous MOFs materials that can selectively capture
CO2 is also of great interest due to the widespread public concern
over global warming and climate change.12a It has been found that
some zeolitic imidazole frameworks (ZIFs) with polar ꢀNO2 group
show high selectivity for capture of CO2 and good stability toward
water.11b Our previous work revealed that 4,4'ꢀbiphenyldicarboxylic
acid (H2BPDC) with two methoxy groups, 2,2'(or 3,3')ꢀdimethoxyꢀ
BPDC, can be used for construction of a series of MOFs with rich
topology structures.13 Our current interest is to incorporate two ꢀNO2
groups into the BPDC backbone at the 2,2'ꢀpositions, and expect that
the ligand, 2,2'ꢀdinitroꢀBPDC (H2L, Scheme 1a) can not only create
robust MOFs with variable structures, but can also endow the MOFs
with interesting properties. It is also noteworthy that only one
example of 2D MOF based solely on H2L ligand has recently been
reported,14 albeit a few other MOFs based on the same ligand, but
with the help of Nꢀcontaining coꢀligands, are known.15 On the basis
of these considerations, we present herein the first 3D MOF
2,2'-dinitrobiphenyl-4,4'-dicarboxylic acid, DMA
=
-
dimethylacetamide) shows unprecedented irreversible
solvent-induced substitutions of bridging aqua ligands and
guest-exchanges in single-crystal-to-single-crystal (SCSC)
transformations at room temperature (RT), producing
quantitatively three daughter crystals, [Cu3L2(ꢀ3-OH)2]·2S (2:
2A, S = acetone; 2B, S = 2-propanol; 2C, S = 2-butanol) which
exhibit reversible interconversion by guest-exchanges at RT
in SCSC transformations. MOF 1 shows excellent separation
selectivity (128) of CO2/N2 at RT and is a better sorbent of
micro-solid-phase extraction (
benchmark ZIF-8.
µ-SPE) than currently known
Metalꢀorganic frameworks (MOFs) have gained increasing attention
due to their variety of topological architectures1 and potential
applications in gas storage, separation, and catalysis.2 Among
crystalline MOFs, SCSC transformation is a particularly interesting
phenomenon that has attracted considerable attention in recent years
since the process can directly provide the accurate relationship
between the structures and properties.3 In general, SCSC
transformation can be induced by external stimuli such as light,4
heat,5 and guest molecules.6 During the SC–SC transformation, a
significant rearrangement of molecular components in the crystals
often takes place, resulting in changes of space group of single
crystal and the coordination sphere of metal ions,7 thus the
reservation of space group is not so common.8 Because the loss of
single crystallinity occurs quite often after a drastic solidꢀstate
rearrangement of atoms, exploration of new MOFs that can endure
the SC–SC transformations still remains a challenge. In porous 3D
MOFs, water molecules are often used as terminal or bridging
[Cu3L2(ꢀ3ꢀOH)2(ꢀ2ꢀH2O)]ꢁ2DMA (1) based on H2L ligand without
any Nꢀcontaining coꢀligand. Remarkably, 1 can undergo irreversible
solventꢀinduced SCSC transformations at RT when soaked in
acetone, 2ꢀpropanol and 2ꢀbutanol, respectively, involving
intramolecular substitution of
by external solvent molecules. The SCSC transformations produce
3ꢀOH)2]ꢁ2S (2A, S =
ꢀ2ꢀH2O ligands and guestꢀexchanges
ligands.8b,9 By use of heat at a suitable temperature, loss of the quantitatively three novel 3D MOFs: [Cu3L2(
ꢀ
terminal water ligands in 3D MOFs can occur in a SCSC acetone; 2B, S = 2ꢀpropanol; 2C, S = 2ꢀbutanol) with their space
transformation but removal of the bridging aqua ligands is more groups being intact (Table S1, ESI†). Furthermore, reversible SCSC
difficult.10 Until now, there has been only one report on SCSC transformations by guestꢀexchanges among 2A, 2B and 2C also take
place at RT with their space groups all remaining unchanged
transformation involving substitution of
ꢀ2ꢀbridging H2O by an
external solvent molecule through simultaneous bond breaking and (Scheme 1b). Such a solventꢀinduced substitution of
ꢀ2ꢀH2O ligands
in SCSC transformations at RT is unprecedented for the 3D
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MOFs.6,10 In addition, 1 is a multifunctional microporous material in guest molecules (Fig. S5, S6, ESI†). Because 2Aꢀ2C have similar
due to its excellent separation selectivity of CO2/N2, good stability structural frameworks, herein, only the structure of 2A is discussed
toward water and higher efficiency than the bestꢀknown ZIFꢀ8 as a in details. The asymmetric unit (Fig. S4, ESI†) of 2A consists of
three Cu2+ ions, two L2– ligands, two 3ꢀOH– ions and two acetone
ꢀ
sorbent of µꢀSPE.
molecules. Both Cu1 and Cu2 adopt elongate octahedral geometries
(Table S4, ESI†), while Cu3 is located at a trigonal bipyramid
geometry. Two
trinuclear [Cu3(
interconnected by the
nanosized ribbon [Cu3(
ꢀ
3ꢀOH– ions cap the triangular Cu3 faces to form a
ꢀ
3ꢀOH)2(ꢀCO2)2]2+ core (Fig. 1) which are
1,1,3ꢀCO2– bridges to form another infinite 1D
3ꢀOH)2(ꢀCO2)4]n (7 Å) along the c axis (Fig.
ꢀ
ꢀ
2b). The 1D nanosized ribbon is further linked through the biphenyl
groups of L2– ligands to generate a 3D network with 1D rectangle
channels of 10.723 × 9.958 Å2 (excluding van der Waals radii) along
the c axis (Fig. 2c). These channels have 41% solvent accessible
voids filled with acetone molecules (Fig. S5, ESI†). These features
are very similar to those observed in 1. However, two significant
changes occurred during the SCSC transformation from 1 to 2A: (1)
Scheme 1 (a) Structure of ligand H2L. (b) Irreversible SCSC
transformations between and ), and reversible SCSC
transformations among 2A 2B and 2C
1
2(A, B, C
,
.
Solvothermal reaction of Cu(NO3)2·3H2O and H2L with a metalꢀ
ligand ratio 3:2 in a binary solvent of DMA/H2O led to the formation
of 1 in 73.3% yield. Structural analysis reveals that 1 crystallizes in
P21/c space group and the asymmetric unit (Fig. S1, ESI†) consists
all the ꢀ2ꢀH2O molecules in 1 are completely removed in 2A, (2) all
the DMA in 1 have been totally replaced by acetone in 2A as also
confirmed by IR with the –C=O vibration of acetone appearing at
1737 cmꢀ1 (Fig. S9, ESI†). The changes directly result in a prominent
decrease of the b axis in unit cell dimensions (34.135 Å in 1 vs.
32.500 Å in 2A, Table S1, ESI†) and an indirect decrease of the 1D
ribbon’s width (8 Å in 1 vs. 7 Å in 2A, Fig. 2a, 2b). Most
importantly, an intrachain substituted reaction happens, resulting in a
remarkable alteration of the local coordination environments of Cu1
of three Cu2+ ions, two L2– ligands, two
ꢀ
3ꢀOH– ions, one
ꢀ2ꢀH2O
and two DMA molecules. Both Cu1 and Cu2 are sixꢀcoordinated by
a water molecule (O1W), two ꢀ
3ꢀOH– ions (O1i and O6) and three
carboxyl oxygen atoms (O4iii, O5ii, O18iv for Cu1 and O3, O15, O16i
for Cu2) with elongate octahedral geometries because the apical Cuꢀ
O bond lengths [2.449(5)ꢀ2.628(5) Å] are significantly longer than
the basal ones [1.905(5)ꢀ1.994(4) Å] (Table S3, ESI†), while Cu3 is
and Cu2 in 2A. The ꢀ2ꢀH2O (O1W) molecules between Cu1 and Cu2
in 1 have been completely substituted by the adjacent uncoordinated
carboxylate oxygen atoms (O17) via the formation of new
coordinated bonds (CuꢀO17 in 2A) without change of the
coordination numbers (Fig. 2b). Such a formation of new metal–
carboxylate bonds during the SC–SC transformation without
changing the space group and the coordination numbers of metal
ions has not been observed for Cu(II)ꢀMOFs3,10b,16 though some
examples are known for the MOFs with Zn2+, Cd2+ and Ni2+
ions.7b,8a,17 Among the five reported SC–SC transformations
fiveꢀcoordinated with
a trigonal bipyramid geometry and its
equatorial positions are defined by three carboxyl oxygen atoms
(O2v, O4iii and O16) and the axial positions are occupied by two
ꢀ3ꢀ
OH– ions (O1 and O6). Notably, the equatorial Cu3ꢀO distances
[2.016(5)ꢀ2.215(4) Å] are slightly longer than the axial ones
[1.908(4)ꢀ1.926(4) Å]. Three Cu2+ ions are linked together by
OH– ions and carboxyl groups to afford a novel trinuclear [Cu3(
ꢀ
ꢀ
3ꢀ
3ꢀ
OH)2(ꢀCO2)2]2+ motif (Fig. 1). The trinuclear Cu3 motifs are
–
interconnected by a
ꢀ2ꢀH2O and two
ꢀ
1,1,3ꢀCO2 bridges to form an
involving release of
ꢀ2ꢀH2O molecules, four examples were
triggered by heating10aꢀd and the transformation at RT is very rare. In
infinite 1D nanosized ribbon [Cu3(
ꢀ3ꢀOH)2(
ꢀ2ꢀH2O)(ꢀCO2)4]n (8 Å)
as rodꢀshaped SBU along the c axis (Fig. 2a). These 1D nanosized
ribbons are further connected by the biphenyl groups of L2– ligands
forming a 3D framework (Fig. 2c). There are 1D rectangle channels
of 10.864 × 10.484 Å2 (excluding van der Waals radii) in 1 along the
c axis (Fig. S2b, ESI†), which possess 40.2% solvent accessible
voids occupied by DMA guest molecules (Fig. S2a, ESI†).
2012, Sun et al. reported the example of SCSC transformations in a
2D MOF involving substitution of
RT.10e In that case, however, the SCSC transformation only involves
replacements of the 2ꢀH2O ligands by the external solvents (MeOH
ꢀ2ꢀH2O ligands by solvents at
ꢀ
or DMSO) concomitant with change of space group, but no
intramolecular substituted reaction occurs. To the best of our
knowledge, the present SCSC transformation induced by the external
solvents at RT involving loss of ꢀ2ꢀH2O ligands and formation of
new metal–carboxylate bonds without changing the space group is
unprecedented. The unique structural transformation observed
between 1 and 2 could be due to four reasons: (i) Cu(II) has variable
coordination geometries and its JahnꢀTeller’s effect can facilitate the
1D nanosized ribbon distortion;10e (ii) the H2L ligands possess a
flexible conformation (see change of the dihedral angles in Table S5,
ESI†) and versatile coordination modes (Scheme S2, ESI†); (iii) the
special topochemical geometry in 1. The uncoordinated carboxylate
Fig. 1 The [Cu3(ꢀ 1 and 2A.
3ꢀOH)2(ꢀCO2)2]2+ motif in
oxygen atoms (O17) are close to the
Å)10b and the axial CuꢀO1W bonds are weak [CuꢀO1W = 2.449(5),
2.628(5) Å]; (iv) hydrogen bond interactions between 2ꢀH2O and
ꢀ2ꢀH2O (O17···O1W = 4.794(3)
Single crystals of 1 (mother) exhibit a visible color change from
lightꢀblue to lightꢀgreen (Fig. S3, ESI†) when immersed at RT in
acetone, 2ꢀpropanol and 2ꢀbutanol, respectively, producing
quantitatively three daughter single crystals, 2Aꢀ2C with a general
formula of [Cu3L2(ꢀ3ꢀOH)2]ꢁ2S (2: 2A, S = acetone; 2B, S = 2ꢀ
propanol; 2C, S = 2ꢀbutanol). All the three new crystals 2Aꢀ2C
adopt the same space group of 1 (Table S1, ESI†) and differ mainly
ꢀ
DMA molecules may act as a ‘doubleꢀedged sword’. On one hand,
the intermolecular O1WꢀH1W···O hydrogen bond interactions in 1
(Fig. S7 and Table S6, ESI†) are helpful to the formation of the 1D
nanosized ribbon and result in higher stability of the 3D framework
before the SCSC transformation. On the other hand, the interactions
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Fig. 2 The infinite 1D nanosized ribbon in
1
(a) and in 2A (b). The significant changes from
1
to 2A are highlighted. (c) The 3D
frameworks of and 2(A, B, C) with 1D channels filled with solvent molecules shown in a ballꢀstick model along the c axis.
1
can also weaken the axial CuꢀO1W bonds to some extent as soon as
some polar solvents capable of forming hydrogenꢀbonding (acetone,
2ꢀpropanol and 2ꢀbutanol) approach. The weakness of the axial Cuꢀ
50
40
30
20
10
0
50
40
30
20
10
0
MOF 2A
MOF 1
O1W bonds would be more beneficial to the removal of the ꢀ2ꢀH2O
CO2 273K
and a shift of the adjacent uncoordinated carboxylate when the
SCSC transformation can take place (a possible mechanism is
proposed in ESI as a PPT file). Furthermore, the motif and polarity
of the external guest molecules also play an important role because
only the structural motif similar to ‘Y’ꢀtype polar solvents such as
acetone, 2ꢀpropanol and 2ꢀbutanol can induce the irreversible SCSC
transformations of 1 to 2(A, B, C), while the other solvents like
CH2Cl2, CHCl3, CH3CN, CH3OH, C2H5OH, nꢀC3H7OH and nꢀ
C4H9OH cannot initiate the transformations. Such a selective guestꢀ
responsive SCSC transformation may find potential applications in
substrateꢀtriggered sensor or shapeꢀselective separation of positional
isomers such as C3 or C4 alcohols.18 Further study on this field is
currently in progress.
CO2 273K
CO2 298K
N2 273K
N2 298K
CO2 298K
N2 273K
N2 298K
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
P/P0
Fig. 3 Gas sorption isotherms for
1 and 2A at 273 and 298 K.
Solid symbols: adsorption; open symbols: desorption.
The pores of 1 and 2A are densely functionalized with polar nitro
groups directly exposed to channels (Fig. 2c). This unique feature
prompted us to examine their CO2 adsorption properties. The
adsorption isotherms of CO2 and N2 for 1 and 2A were measured up
to 1 bar at 273 and 298 K, respectively. As shown in Fig. 3, the CO2
and N2 uptake values of 1 were 47.1 and 1.33 cm3/g at 273 K, and
32.5 and 0.52 cm3/g at 298 K, respectively, while the corresponding
values of 2A were 47.6 and 2.9 cm3/g at 273 K, and 37.2 and 1.5
cm3/g at 298 K, respectively. According to the conventional
calculated method of initial slopes of adsorption isotherms,19 the
selective separation ratio of CO2/N2 for 1 is 149 at 273 K and 128 at
298 K (Fig. S13, ESI†), while the corresponding value for 2A is 116
at 273 K and 92 at 298 K (Fig. S14, ESI†). To our knowledge, the
present separation selectivity of CO2/N2 for 1 is the highest value
reported until now for MOFs materials at low pressures and under
singleꢀgas source conditions (Table S8, ESI†).12a,19 This apparent
selectivity for CO2 is presumably attributed to the interactions
Notably, the daughter crystals 2Aꢀ2C can be randomly
interconverted (Fig. 2c) in SCSC fashion quantitatively by reversible
guestꢀexchanges at RT without changes of space group and color
(Table S2 and Fig. S3, ESI†). For example, dipping 2A in 2ꢀ
propanol for one day affords 2B quantitatively, and when the crystal
of 2B is dipped in acetone for one day, 2A is regenerated
quantitatively. This type of reversible interconversion among 2A-2C
through guestꢀexchange SCSC transformations at RT is quite
rare,8b,10e and can be used to synthesize novel crystalline MOFs
materials easily and quantitatively. Notably, none of the MOFs 2Aꢀ
2C could be obtained by direct solvothermal synthesis.
The experimental PXRD patterns of 1 and 2A are basically
identical to the respective simulated patterns, indicating the high
phase purity of the bulk products of 1 and 2A (Fig. S10, ESI†).
When the crystals of 1 are immersed in water for one day, their peak
positions are in good agreement with the simulated ones, revealing
their good stability in water which is seldom observed in the
carboxylateꢀbased porous 3D MOFs materials.12 The TGA curves
(Fig. S11, ESI†) of 1 and 2A show that the weight loss of 17.0% is
observed from 38 to 253°C for 1 due to the loss of two DMA
between CO2 and the rich functional groups (–NO2, ꢀ
3ꢀOH– and free
–CO2 ) existed in 1.11b,12a,15g The high CO2/N2 separation selectivity
and good water stability make 1 as a promising candidate for
industrial postꢀcombustion gas separation application.
–
molecules and one coordinated ꢀ2ꢀH2O (calculated 17.9%), and for
2A, the weight loss of 10.6% occurs from 38 to 194°C due to the
loss of two acetone molecules (calculated 11.6%).
To investigate the permanent porosity, 1 and 2A were activated to
obtain the fully evacuated framework. The N2 adsorption isotherm of
the guestꢀfree samples at 77
K exhibited reversible typeꢀI
characteristics with a saturation uptake of 127 cm3/g for 1 and 190
cm3/g for 2A (Fig. S12, ESI†). The estimated BrunauerꢀEmmettꢀ
Teller (BET) surface area was 395 m2/g for 1 and 596 m2/g for 2A
based on the N2 sorption isotherm.
Fig. 4 Comparison of the normalized extraction efficiencies of
1
, ZIFꢀ8 and commercial
µꢀSPE sorbents for five estrogens.
The error bar shows standard deviation of the mean.
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The good water stability and suitable pore size of 1 encouraged us
to further study its possibility serving as a sorbent material for µꢀ
SPE, a highly effective sample pretreatment and enrichment method
for aqueous samples.20 Our preliminary experimental results indicate
that 1 shows higher extraction efficiency for five estrogens (Scheme
S3, ESI†) than ZIFꢀ8 (Fig. 4). Furthermore, no decrease of extraction
performance was observed even after more than 10 replicated
extractions (Table S9, ESI†). The PXRD peak positions of 1 after 10
extraction processes are in agreement with the asꢀsynthesized ones
(Fig. S10, ESI†), indicating an exceptional chemical stability of 1 in
the µꢀSPE experiments. Such excellent performance of 1 may result
from its larger pore (12.7 Å) with bigger aperture (6.6 Å) than ZIFꢀ8
(11.6 Å; 3.4 Å) and the possible hydrogen bonding interactions
Ohba and S. Kitagawa, Angew. Chem., Int. Ed., 2008, 47, 8843; (
Y. Fu, J. Su, S. Yang, Z. Zou, G. Li, F. Liao, M. Xiong and J. Lin,
Cryst. Growth Des., 2011, 11, 2243; ( ) D. L. Reger, A. Leitner, M.
D. Smith, T. T. Tran and P. S. Halasyamani, Inorg. Chem., 2013, 52
10041; ( ) G.ꢀC. Lv, P. Wang, Q. Liu, J. Fan, K. Chen and W.ꢀY.
Sun, Chem. Commun., 2012, 48, 10249.
11 ( ) P. Küsgens, M. Rose, I. Senkovska, H. Fröde, A. Henschel, S.
Siegle and S. Kaskel, Microporous Mesoporous Mater., 2009, 120
325; ( ) R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M.
O’Keeffe and O. M. Yaghi, J. Am. Chem. Soc., 2009, 131, 3875.
12 ( ) Q. Yang, S. Vaesen, F. Ragon, A. D. Wiersum, D. Wu, A. Lago,
c)
d
,
e
a
,
b
a
–
T. Devic, C. Martineau, F. Taulelle, P. L. Llewellyn, H. Jobic, C.
between the functional groups (–NO2 and free –CO2 ) in 1 and
phenol group in the estrogens (Fig. S15, ESI†).20
Zhong, C. Serre, G. D. Weireld and G. Maurin, Angew. Chem., Int.
In summary, we have synthesized a smart singleꢀcrystal (
by using a dinitroꢀsubstituted aromatic dicarboxylate ligand.
exhibits an unprecedented irreversible solventꢀinduced SC–SC
transformation involving substitution of bridging water at RT
through guest exchanges with acetone, 2ꢀpropanol, 2ꢀbutanol,
1)
1
Ed., 2013, 52, 10316; (b) Q. Chen, Z. Chang, W.ꢀC. Song, H. Song,
H.ꢀB. Song, T.ꢀL. Hu and X.ꢀH. Bu, Angew. Chem., Int. Ed., 2013,
52, 11550.
13 (
X.ꢀK. Ke and L.ꢀM. Peng, Cryst. Growth Des., 2010, 10, 887; (
J. Zhang, X.ꢀZ. Wang, D.ꢀR. Zhu, Y. Song, Y. Xu, H. Xu, X. Shen,
T. Gao and M.ꢀX. Huang, CrystEngComm, 2011, 13, 2586; ( ) H.
Xu, W. Bao, Y. Xu, X. Liu, X. Shen and D. Zhu, CrystEngComm
2012, 14, 5720; ( ) R. Luo, H. Xu, H.ꢀX. Gu, X. Wang, Y. Xu, X.
Shen, W. Bao and D.ꢀR. Zhu, CrystEngComm, 2014, 16, 784.
a
) X.ꢀZ. Wang, D.ꢀR. Zhu, Y. Xu, J. Yang, X. Shen, J. Zhou, N. Fei,
b
) H.ꢀ
producing quantitatively three daughter crystals (2A
ꢀ2C). The
2A 2C can also be quantitatively interconverted in SCSC
ꢀ
fashion by reversible guestꢀexchange at RT. The good water
and chemical stability, excellent separation selectivity of CO2
over N2 at RT, and higher extraction efficiency than ZIFꢀ8 as a
c
,
d
sorbent of
µꢀSPE make 1 as a potential multifunctional
microporous MOF material.
14 J.ꢀY. Zhang, X.ꢀB. Li, K. Wang, Y. Ma, A.ꢀL. Cheng and E.ꢀQ. Gao,
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21171093, 21476115,
51109062).
Dalton Trans., 2012, 41, 12192.
15 (
Cryst. Growth Des., 2011, 11, 3681; (
X. Zhou, J. Hua, Z. Shi and S. Feng, CrystEngComm, 2011, 13, 1291;
) B. Li, Y. Zhang, G. Li, D. Liu, Y. Chen, W. Hu, Z. Shi and S.
Feng, CrystEngComm, 2011, 13, 2457; ( ) B. Li, X. Zhou, Q. Zhou,
G. Li, J. Hua, Y. Bi, Y. Li, Z. Shi and S. Feng, CrystEngComm
2011, 13, 4592; ( ) J.ꢀY. Zhang, Y. Ma, A.ꢀL. Cheng, Q. Yue, Y. Q.
Sun and E.ꢀQ. Gao, Dalton Trans., 2011, 40, 7219; ( ) B. Li, F. Yang,
Y. Zhang, G. Li, Q. Zhou, J. Hua, Z. Shi and S. Feng, Dalton Trans.
a
) J.ꢀY. Zhang, X.ꢀH. Jing, Y. Ma, A.ꢀL. Cheng and E.ꢀQ. Gao,
Notes and references
b
) B. Li, G. Li, D. Liu, Y. Peng,
a
State Key Laboratory of MaterialsꢀOriented Chemical Engineering,
College of Chemistry and Chemical Engineering, Nanjing Tech
(c
University, Nanjing, 210009, China
d
b College of Environment, Hohai University, Nanjing, 210098, China
† Electronic Supplementary Information (ESI) available. CCDC 977429ꢀ
977438. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/b000000x/
,
e
f
,
,
‡ These authors contributed equally to this work.
2012, 41, 2677; (g) P. V. Dau and S. M. Cohen, CrystEngComm
1
2
3
4
M. O’Keeffe and O. M. Yaghi, Chem. Rev., 2012, 112, 675.
Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2012, 112, 1126.
J. J. Vittal, Coord. Chem. Rev., 2007, 251, 1781.
2013, 15, 9304.
16 N. Masciocchi, S. Galli, G. Tagliabue, A. Sironi, O. Castillo, A.
Luque, G. Beobide, W. Wang, M. A. Romero, E. Barea and J. A. R.
Navarro, Inorg. Chem., 2009, 48, 3087.
D. Liu, Z.ꢀG. Ren, H.ꢀX. Li, J.ꢀP. Lang, N.ꢀY. Li and B. F.
Abrahams, Angew. Chem., Int. Ed., 2010, 49, 4767.
T. Pretsch, K. W. Chapman, G. J. Halder and C. J. Kepert, Chem.
Commun., 2006, 1857.
17 (a) M. Nagarathinam and J. J. Vittal, Chem. Commun., 2008, 438; (b)
5
6
A. CalderónꢀCasado, G. Barika, B. Bazán, M.ꢀK. Urtiaga, O.
Vallcorba, J. Rius, C. Miravittles and M.ꢀI. Arriortua,
CrystEngComm, 2011, 13, 6831.
(a
) M. K. Sharma and P. K. Bharadwaj, Inorg. Chem., 2011, 50
,
1889; (
b
) X.ꢀP. Zhou, Z. Xu, M. Zeller, A. D. Hunter, S. S.ꢀY. Chui
18 (
D. J. Adams and A. I. Cooper, Nature Chem., 2012,
Jacobs, G. O. Lloyd, J. A. Gertenbach, K. K. MuellerꢀNederbock, C.
Esterhuysen and L. J. Barbour, Angew. Chem., Int. Ed., 2012, 51
a
) T. Mitra, K. E. Jelfs, M. Schmidtmann, A. Ahmed, S. Y. Chong,
and C.ꢀM. Che, Inorg. Chem., 2011, 50, 7142.
5
, 276; ( ) T.
b
7
8
L. Wen, P. Cheng and W. Lin, Chem. Commun., 2012, 48, 2846.
(a
) J. D. Ranford, J. J. Vittal and D. Wu, Angew. Chem., Int. Ed.
,
,
1998, 37, 1114; (
b
) M. C. Das and P. K. Bharadwaj, J. Am. Chem.
4913; (c) Y. Takashima, V. M. Martínez, S. Furukawa, M. Kondo, S.
Shimomura, H. Uehara, M. Nakahama, K. Sugimoto and S.
Soc., 2009, 131, 10942.
9
X.ꢀY. Dong, B. Li, B.ꢀB. Ma, S.ꢀJ. Li, M.ꢀM. Dong, Y.ꢀY. Zhu, S.ꢀQ.
Kitagawa, Nature Commun., 2011, 2, 168.
Zang, Y. Song, H.ꢀW. Hou and T. C. W. Mak, J. Am. Chem. Soc.
2013, 135, 10214.
,
19 J. An, S. J. Geib and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 38.
20 Y. Wang, S. Jin, Q. Wang, G. Lu, J. Jiang and D. Zhu, J.
Chromatogr. A, 2013, 1291, 27.
10 (a) D.ꢀX. Xue, W.ꢀX. Zhang, X.ꢀM. Chen and H.ꢀZ. Wang, Chem.
Commun., 2008, 1551; (b) S. K. Ghosh, W. Kaneko, D. Kiriya, M.
4 | J. Name., 2012, 00, 1-3
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