Interpenetrated metal-organic framework with selective gas adsorption and luminescent properties

Article abstract of DOI:10.1021/cg500269h

A new 2-fold interpenetrated cadmium metal-organic framework {[Cd ₂(TPPBDA)(OBA)₂]·4DMA·8H₂O} _n (1) (Cd-MOF) (TPPBDA = N,N,N',N'-tetrakis(4-(4-pyridine)-phenyl) biphenyl-4,4'-diamine, H₂OBA = 4,4'-oxybis(benzoate), and DMA = N,N-dimethylacetamide) was synthesized by a solvothermal reaction. Compound 1 is a 3D net with a meso-helical chain. A noticeable structural feature is that the arrangement of lattice DMA molecules is different in the different meso-helical channels. The material exhibits gas sorption properties for CO₂, H₂, and CH₄. The adsorption selectivity of CO ₂/CH₄ was calculated from the single-component isotherms using the dual-site Langmuir-Freundlich-based ideal adsorbed solution theory. In addition, the luminescent properties of the Cd-MOF in the solid state and in suspension in different organic solvents was investigated.

Full text of DOI:10.1021/cg500269h

Article
pubs.acs.org/crystal
Interpenetrated Metal−Organic Framework with Selective Gas
Adsorption and Luminescent Properties
Ling Qin,† Ze-Min Ju,† Zhong-Jie Wang,‡ Fan-Dian Meng,† He-Gen Zheng,*,† and Jin-Xi Chen*,‡
†State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of
Microstructures, Nanjing University, Nanjing 210093, PR China
‡School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, PR China
S
* Supporting Information
ABSTRACT: A new 2-fold interpenetrated cadmium metal−organic framework
{[Cd2(TPPBDA)(OBA)2]·4DMA·8H2O}n (1) (Cd-MOF) (TPPBDA = N,N,N′,N′-tetrakis(4-
(4-pyridine)-phenyl)biphenyl-4,4′-diamine, H2OBA = 4,4′-oxybis(benzoate), and DMA = N,N-
dimethylacetamide) was synthesized by a solvothermal reaction. Compound 1 is a 3D net with a
meso-helical chain. A noticeable structural feature is that the arrangement of lattice DMA
molecules is different in the different meso-helical channels. The material exhibits gas sorption
properties for CO2, H2, and CH4. The adsorption selectivity of CO2/CH4 was calculated from the
single-component isotherms using the dual-site Langmuir−Freundlich-based ideal adsorbed
solution theory. In addition, the luminescent properties of the Cd-MOF in the solid state and in
suspension in different organic solvents was investigated.
topological analysis, absorption performance and photo-
luminescent properties are studied in detail. The X-ray
structure reveals that compound 1 is a doubly interpenetrated
3D network.
INTRODUCTION
■
Metal−organic frameworks (MOFs) have attracted tremendous
attention because of their ability to adjust their porosity and
because of the functionalities that are incorporated in the
frameworks.1 As a result, numerous MOFs have been designed
and synthesized for potential applications including gas storage
and separation, nonlinear optics, magnetics, and catalysis.2
Some properties, for example, gas sorption separation, depend
mainly on pore size and shape, which is known as the molecular
sieving effect.3 Zhou and co-workers reported an inter-
penetrated and porous net, PCN-17.4 The interpenetration
and sulfate bridging in PCN-17 reduce its pore size to
approximately 3.5 Å, leading to selective adsorption of H2 and
O2 over N2 and CO. Therefore, this material can be used for
the separation of N2 and O2, H2 and CO, and N2 and H2.4
However, some other properties may depend on the
composition of the MOFs, such as sensing.5 For example, our
group reported a rare nanotubular MOF that was constructed
from the ligand 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, in which
the tetrazine ring plays the role of chromophore and exhibits a
solvatochromic response to different solvent guest molecules.6
Thus, more and extensive efforts have been devoted to
synthesizing porous MOFs because of their potential
applications.
EXPERIMENTAL SECTION
■
General Methods. All chemicals and solvents used in the
syntheses were of reagent grade and used without further purification.
H2OBA was used as commercially available. The TPPBDA ligand was
prepared as follows on the basis of palladium-catalyzed cross-coupling
reaction.
Preparation of N,N,N′,N′-Tetrakis(4-bromophenyl)biphenyl-
4,4′-diamine. An oven-dried 500 mL Schlenk flask was charged with
tris(4-bromophenyl)amine (24.1 g, 50 mmol), and then ether (350
mL) and N,N,N′,N′-tetramethylethylenediamine (8.2 mL) were added
through a rubber septum. The reaction mixture was cooled to −78 °C.
Upon slow addition of a n-BuLi solution (34 mL, 1.6 M in hexanes, 55
mmol), the mixture was stirred for 1 h at −78 °C. Solid CuCl2 (10.8 g,
80 mmol) was added, and the reaction mixture was then allowed to
warm slowly to room temperature and stirred for an additional 10 h.
The reaction mixture was exposed to air, stirred for 30 min, and
concentrated in vacuo. Chloroform (100 mL) and water (100 mL)
were added, and the layers were separated. The aqueous layer was
subsequently washed with chloroform (50 mL) three times. The
organic extracts were combined, dried with MgSO4, and filtered. The
volatile chloroform was removed under vacuum to leave a green solid.
Purification by column chromatography (petroleum ether) yielded the
pure product as a white solid (10.1 g, 50%). 1H NMR (DMSO-d6, 500
MHz, 25 °C): 7.61 (d, 4H), 7.5 (d, 8H), 7.09 (d, 4H), 7.0 (d, 8H).
Many Cd-based MOFs have been reported in the literature;7
herein, we describe a new 2-fold interpenetrated framework
{[Cd2(TPPBDA)(OBA)2]·4DMA·8H2O}n (1) based on Cd-
(II), tetratopic pyridyl ligand N,N,N′,N′-tetrakis (4-(4-
pyridine)-phenyl)biphenyl-4,4′-diamine (TPPBDA), and a
bent carboxylate ligand (H2OBA = 4,4′-oxybis(benzoate),8
DMA = N,N-dimethylacetamide). The crystal structure,
Received: December 10, 2013
Revised: April 25, 2014
Published: April 30, 2014
© 2014 American Chemical Society
2742
dx.doi.org/10.1021/cg500269h | Cryst. Growth Des. 2014, 14, 2742−2746

Crystal Growth & Design
Article
Scheme 1. Neutral Tetradentate Ligand TPPBDA and Bent Carboxylate Co-ligand H2OBA
Figure 1. Coordination environment of the Cd(II) ions in 1 (hydrogen atoms and uncoordinated DMA and water molecules are omitted for clarity;
30% ellipsoid probability); symmetry codes: no. 1 = −1/2 + x, 1/2 − y, 1/2 + z; no. 2 = 1/2 + x, 1/2 − y, 1/2 + z; no. 3 = 1 − x, −y, −z; and no. 4 =
1
−1/2 + x, /2 − y, −1/2 + z. (b) View of 3D framework of 1 along the a axis.
Preparation of N,N,N′,N′-Tetrakis(4-(4-pyridine)-phenyl)-
biphenyl-4,4′-diamine (TPPBDA). A 500 mL Schlenk flask was
evacuated, backfilled with nitrogen, and charged with N,N,N′,N′-
tetrakis(4-bromophenyl)biphenyl-4,4′-diamine (8 g, 10 mmol),
pyridine-4-boronic acid (8.41 g, 70 mmol), and K2CO3 (9.66 mg, 70
mmol). The flask was evacuated and backfilled with nitrogen, and
Pd(PPh3)4 (2.2 mg, 0.05 mmol, 5.0 mol %) and 1,4-dioxane/H2O (v/v
= 3:2) were then added through a rubber septum. The reaction
mixture was heated at 95 °C with stirring until the starting N,N,N′,N′-
tetrakis(4-bromophenyl)biphenyl-4,4′-diamine was completely con-
sumed, as determined by TLC. The reaction mixture was then cooled
to room temperature, and 1,4-dioxane was removed under vacuum.
The aqueous mixture was extracted with chloroform (50 mL). The
combined organic layers were dried over anhydrous MgSO4, filtered,
and concentrated in vacuo. The crude material was purified by
chromatography on silica gel (ethyl acetate/methanol = 10:1), yielding
the pure product as a yellow solid (4.2 g, 53%). 1H NMR (DMSO-d6,
500 MHz, 25 °C): 8.60 (s, 8H), 7.80 (d, 8H), 7.68 (s, 12H), 7.19 (d,
12H). 13C NMR (DMSO-d6): 119.42, 120.41, 121.04, 124.33, 125.63,
128.15, 128.53, 131.85, 135.50, 145.91, 146.65, 148.12, 150.67. MS
(ESI-TOF): calcd for C56H40N6, 796; found, 797.
5.39; N, 6.88. The IR spectra of the corresponding complex is shown
in Supporting Information Figure S8.
RESULTS AND DISCUSSION
■
Crystal Structure of {[Cd2(TPPBDA)(OBA)2]·4DMA·
8H2O}n (1). Compound 1 crystallizes in the monoclinic crystal
system with two Cd cations in the asymmetric unit (Figure 1a).
(Crystal data and structure refinement parameters of
compound 1 are given in Table 1.) Each Cd(II) unit has a
[CdN2O5] coordination geometry. The OBA2− ligand takes
bidentate-chelation and μ3-chelating-bridging tridentate coor-
dination modes; two Cd(II) ions are bridged by two
carboxylate O atoms, forming a four-membered square-shaped
[Cd2(CO2)4] ring. The OBA2− anions connect to the
[Cd2(CO2)4] units to form 1D chains. Then, the chains are
linked by the neutral tetradentate ligand to generate a 3D net
(Figure 1b). It is worth noting that different shapes of channels
are generated on the ab, bc, and ac planes in the individual
network, as shown in Supporting Information Figure S1.
Compound 1 is a 3D net composed of meso-helical chains
with a long pitch of 21.115 Å, which are labeled as the L1 and
R1 chains (Figure 2a). The two symmetrically related helices
coexist in the centrosymmetric solid, in which they appear in
the left-handed and right-handed enantiomorphs, respectively.
However, the L1- and R1-type single meso-helical chains are
arranged alternatively, which indicates achirality and is further
confirmed by the achiral space group, C2/c. The central axis
Synthesis of Complex 1. Compound 1 was synthesized by
dissolving 39.8 mg of TPPBDA and 25.8 mg of H2OBA in DMA (3
mL). A solution of 0.1 mmol aqueous Cd(NO3)2 was then added, and
the mixture was placed in a Teflon vessel within an autoclave and
heated at 85 °C for 3 days. Pale yellow prismatic crystals were
obtained, filtered off, and dried under ambient conditions. The yield of
the reaction was ca. 50% based on the TPPBDA ligand. Anal Calcd. for
C100H108Cd2N10O22: C, 59.62; H, 5.37; N, 6.91. Found: C, 59.24; H,
2743
dx.doi.org/10.1021/cg500269h | Cryst. Growth Des. 2014, 14, 2742−2746

Crystal Growth & Design
Article
Table 1. Crystal Data and Structure Refinement Parameters
of Compound 1
c
compound
empirical formula
formula weight
crystal system
space group
a (Å)
1
C92H74Cd2N8O12
1708.39
monoclinic
C2/c
21.1146(11)
37.6435(19)
28.2514(14)
90
b (Å)
c (Å)
α (deg)
Figure 3. (a) Schematic representation of (4,6)-connected topology
net. (b) Schematic view of the 2-fold interpenetrating framework.
β (deg)
108.8030(10)
90
γ (deg)
V (Å3)
21256.6(19)
8
Z
Dcalcd (g cm−3
)
1.068
μ (mm−1
)
0.452
F(000)
6992
tot., uniq. data
R(int)
59 725, 18 710
0.0715
observed data [I > 2σ(I)]
Nref, Npar
10 839
18 710, 1029
0.0391, 0.0820
1.035
a
b
R1 , wR2 [I > 2σ(I)]
GOF on F2
min and max resd density (e Å−3
)
−0.391, 0.788
a
b
R1 = Σ||Fo| − |Fc||/|Σ|Fo|. wR2 ={Σ[w(Fo − Fc2)2]/Σ[w(Fo )2]}1/2
;
2
2
c
where w = 1/[σ2(Fo2) + (aP)2 + bP] and P = (Fo + 2Fc2)/3. The
residual electron densities were flattened by using the SQUEEZE
option of PLATON.
2
about each helical chain is a 2-fold screw axis.9 The other
structural feature is that the arrangement of lattice DMA
molecules is different in the different meso-helical channels,
which is attributed to the crystallographic symmetry. It can be
seen that the O atoms of the DMA molecules are oriented
upward in the L1 channels, whereas the O atoms are oriented
downward in the R1 channels, as shown in Figure 2b.
Better insight into the nature of the intricate framework can
be attained by the application of a topological approach,10 that
is, reducing multidimensional structures to a simple node and
connection net. As discussed above, [Cd2(CO2)4] clusters are
defined as 6-connected nodes. Likewise, TPPBDA ligands
ligating with four [Cd2(CO2)4] clusters can act as 4-connected
Figure 4. Gas adsorption isotherms for CO2 (black) and CH4 (red) at
273 K and for H2 (blue) at 77 K.
nodes. On the basis of the simplification principle, the resulting
structure is a (4,6)-connected net with point symbol {46}-
{42.68.85} (Figure 3a). The overall structure is a pair of identical
nets, which are mutually interpenetrated to form a doubly
interpenetrated framework (Figure 3b). Despite the framework
interpenetration, the structure retains a 45.7% solvent-
accessible void volume, as calculated by the PLATON
program.11 TGA reveals a 24% (by mass) loss of solvent,
which is ascribed to the loss of four lattice DMA and eight
water molecules, with a theoretical weight loss of 24.28%; the
Figure 2. (a) View of meso-helical chains (marked by L1 and R1) in net 1. (b) Perspective views of the different arrangement directions of guest
DMA molecules, especially in the L1 and R1 channels. The hydrogen atoms and the squeezed guest molecules are omitted for clarity.
2744
dx.doi.org/10.1021/cg500269h | Cryst. Growth Des. 2014, 14, 2742−2746

Crystal Growth & Design
Article
Information Figure S4. The value of Qst is about 23−25 kJ/mol,
which is similar to the values for some other MOF materials.14
The selectivity of CO2/CH4 was calculated from the
experimental single-component isotherms using the ideal
adsorbed solution theory (IAST) method.15 The dual-site
Langmuir−Freundlich equation was used to fit the exper-
imental data.
b1 × p1/n
1 + b1 × p1/n
b2 × p1/n
1 + b2 × p1/n
1
2
q = qm1
×
+ qm2 ×
1
2
The CO2/CH4 selectivity calculation was based on a CO2/
CH4 mixture with CO2/CH4 = 1:1 at a total pressure of 1 atm.
Adsorption isotherms predicted by IAST suggested that the
dual-site Langmuir−Freundlich equation fit the single-compo-
nent isotherms well, as shown in Figure 5. The r2 (coefficient of
determination) values for all of the fitted isotherms were
0.999995. For 1, CO2 is preferentially adsorbed over CH4
because of the stronger interactions between CO2 and the Cd-
MOF.
Figure 5. IAST-predicted isotherms and selectivity of equimolar
mixtures of CO2 and CH4 in compound 1 at 298 K as a function of
pressure.
Luminescent Properties and X-ray Powder Diffrac-
tion. Phase purity of the bulk material was confirmed by the
comparison of its powder diffraction (PXRD) patterns with
that simulated from single-crystal X-ray diffraction study
(Supporting Information Figure S5). The solid-state emission
spectrum for compound 1 exhibits a broad peak at 553 nm,
which is more likely to be attributed to intraligand transition
because an emission with a maximum at 558 nm is observed for
TPPBDA (Supporting Information Figure S6). Some fluo-
rescent MOF materials that are sensitive to guest solvent
molecules have been reported.16 Motivated by previous works,
the photoluminescent properties were also investigated in
suspension in common solvents. A finely ground sample of
compound 1 (10 mg) was immersed in different organic
solvents (10 mL), treated by ultrasonication for 2 h, and then
aged to form stable emulsions. The solvents tested were N,N-
dimethylformamide (DMF), chloroform (CHCl3), dichloro-
methane (CH2Cl2), acetonitrile (CH3CN), and methanol
(CH3OH). As shown in Figure 6, the PL intensities are
dependent on the solvent molecules, particularly in the case of
DMF and CH2Cl2, which exhibit the most significant enhancing
and quenching effects, respectively. In short, the intensities are
affected by the solvents, with DMF > CH3OH > CH3CN >
CHCl3 > CH2Cl2 (Supporting Information Figure S7), which
decomposition of compound 1 starts at 350 °C (Supporting
Information Figure S2).
Sorption Properties. With an increasing desire to use
porous MOFs in storage applications, gas adsorptions for the
Cd-MOF were measured. Adsorption measurements were
performed on Micromeritics ASAP 2020 M+C surface area
analyzer. Ultra-high-purity grade N2, H2, CO2, and CH4
(>99.999%) were used. All of the measured sorption isotherms
were repeated twice to confirm reproducibility. Low-pressure
H2, CO2, CH4, and N2 adsorption isotherms were measured at
273 and 298 K from 0 to 1 bar. There was little adsorption of
N2 up to 1 atm. The other adsorption data demonstrated that
the compound selectively adsorbed CO2 rather than CH4
(Figure 4). This selective adsorption may be ascribed to the
special quadrupole moment or the smaller gas molecule
diameter of CO2.12 The CO2 adsorption capacity for
compound 1 at 273 and 298 K is shown in Supporting
Information Figure S3. The isosteric heats of adsorption (Qst)
were calculated from the CO2 adsorption isotherms using the
Clausius−Clapeyron equation (for details, see the Supporting
Information).13 A plot of the isosteric heat of adsorption (Qst)
as a function of CO2 adsorbed quantity is shown in Supporting
Figure 6. Left: emission of 1 suspended in various solvents (DMF, CH3OH, CH3CN, CHCl3, and CH2Cl2) under the same testing conditions.
Right: different emission peaks of 1 suspended in DMF or CHCl3; the test conditions in CHCl3 were further optimized to provide better data for
comparison.
2745
dx.doi.org/10.1021/cg500269h | Cryst. Growth Des. 2014, 14, 2742−2746

Crystal Growth & Design
Article
may be ascribed to the different solubility.17 The other
interesting feature is that an emission with a maximum at
458 nm is observed in CHCl3. However, the main emission
peaks are centered at 495 nm in the other four solvents. The
different emission peaks may be ascribed to specific host−guest
recognition.18
(5) (a) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van
Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105. (b) Lu, G.;
Hupp, J. T. J. Am. Chem. Soc. 2010, 132, 7832.
(6) (a) Lu, Z. Z.; Zhang, R.; Pan, Z. R.; Li, Y. Z.; Guo, Z. J.; Zheng,
H. G. Chem.Eur. J. 2012, 18, 2812. (b) Lu, Z. Z.; Zhang, R.; Li, Y.
Z.; Guo, Z. J.; Zheng, H. G. J. Am. Chem. Soc. 2011, 133, 4172.
(7) (a) Sun, L.; Xing, H.; Xu, J.; Liang, Z.; Yu, J.; Xu, R. Dalton Trans.
2013, 42, 5508. (b) Li, C. P.; Du, M. Inorg. Chem. Commun. 2011, 14,
502. (c) Zheng, S. L.; Chen, X. M. Aust. J. Chem. 2004, 57, 703.
(8) (a) Qin, L.; Hu, J. S.; Zhang, M. D.; Guo, Z. J.; Zheng, H. G.
Chem. Commun. 2012, 48, 10757. (b) Mahata, P.; Sundaresan, A.;
Natarajan, S. Chem. Commun. 2007, 43, 4471. (c) Wang, X. L.; Qin,
C.; Wang, E. B.; Li, Y. G.; Su, Z. M.; Xu, L.; Carlucci, L. Angew. Chem.,
Int. Ed. 2005, 44, 5824.
(9) Xu, L.; Qin, C.; Wang, X. L.; Wei, Y. G.; Wang, E. B. Inorg. Chem.
2003, 42, 7342.
(10) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl.
Crystallogr. 2000, 33, 1193.
(11) Spek, A. L. Acta Crystallogr., Sect. A 1990, 46, 194.
(12) (a) Cui, J. H.; Li, Y. Z.; Guo, Z. J.; Zheng, H. G. Chem. Commun.
2013, 49, 555. (b) Xiang, S. C.; He, Y. B.; Zhang, Z. J.; Wu, H.; Zhou,
W.; Krishna, R.; Chen, B. L. Nat. Commun. 2012, 3, 954. (c) Ortiz, G.;
CONCLUSIONS
■
We have successfully prepared a 3D porous network (Cd-
MOF) based on TPPBDA and H2OBA as coligands. The
structure of the Cd-MOF is a doubly interpenetrated
framework with a {46}{42.68.85} net containing meso-helices.
The Cd-MOF exhibits selective gas sorption for CO2 over that
of CH4 and N2. The selectivity of CO2/CH4 was calculated
using the dual-site Langmuir−Freundlich-based ideal adsorbed
solution theory method. Additionally, the luminescent proper-
ties of the Cd-MOF in the solid state and in suspension in
different solvents were investigated.
ASSOCIATED CONTENT
* Supporting Information
■
Brandes
̀
, S.; Rousselin, Y.; Guilard, R. Chem.Eur. J. 2011, 17, 6689.
S
(13) (a) Si, X. L.; Jiao, C. L.; Li, F.; Zhang, J.; Wang, S.; Liu, S.; Li, Z.
B.; Sun, L. X.; Xu, F.; Gabelicad, Z.; Schick, C. Energy Environ. Sci.
2011, 4, 4522. (b) Park, M.; Moon, D.; Yoon, J. W.; Chang, J. S.; Lah,
M. S. Chem. Commun. 2009, 45, 2026.
Crystallographic data in CIF format, selected bond lengths and
angles, IR, TGA, PXRD, patterns of photochemistry, and gas
adsorption data. This material is available free of charge via the
Internet at http://pubs.acs.org.
(14) (a) Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Vimont, A.; Daturi,
M.; Hamon, L.; Weireld, G. D.; Chang, J. S.; Hong, D. Y.; Hwang, Y.
AUTHOR INFORMATION
Corresponding Author
*(H.-G.Z.) E-mail: zhenghg@nju.edu.cn. Fax: 86-25-83314502.
K.; Jhung, S. H.; Fer
Lecroq, L.; Volkringer, C.; Marrot, J.; Fer
F.; Bourrelly, S.; Llewellyn, P. L.; Latroche, M. J. Am. Chem. Soc. 2006,
́
ey, G. Langmuir 2008, 24, 7245. (b) Loiseau, T.;
■
́
ey, G.; Haouas, M.; Taulelle,
128, 10223. (c) Wang, Q. M.; Shen, D.; Bulow, M.; Lau, M. L.; Deng,
̈
Notes
S.; Fitch, F. R.; Lemcoff, N. O.; Semanscin, J. Microporous Mesoporous
The authors declare no competing financial interest.
Mater. 2002, 55, 217.
(15) (a) Karra, J. R.; Grabicka, B. E.; Huang, Y. G.; Walton, K. S. J.
Colloid Interface Sci. 2013, 392, 331. (b) Peng, X.; Cheng, X.; Cao, D.
P. J. Mater. Chem. 2011, 21, 11259. (c) Bae, Y. S.; Mulfort, K. L.; Frost,
H.; Ryan, P.; Punnathanam, S.; Broadbelt, L. J.; Hupp, J. T.; Snurr, R.
Q. Langmuir 2008, 24, 8592.
(16) (a) Sun, C. Y.; Wang, X. L.; Qin, C.; Jin, J. L.; Su, Z. M.; Huang,
P.; Shao, K. Z. Chem.Eur. J. 2013, 19, 3639. (b) Cui, J. H.; Lu, Z. Z.;
Li, Y. Z.; Guo, Z. J.; Zheng, H. G. Chem. Commun. 2012, 48, 7967.
(c) Wang, C.; Lin, W. B. J. Am. Chem. Soc. 2011, 133, 4232. (d) Bauer,
C. A.; Timofeeva, T. V.; Setterstten, T. B.; Patterson, B. D.; Liu, V. H.;
Simmons, B. A.; Allendorf, M. D. J. Am. Chem. Soc. 2007, 129, 7136.
(17) Song, J.; Zhou, Z.; Dong, X.; Huang, H.; Cao, D.; Liang, L.;
Wang, K.; Zhang, J.; Chen, F. X.; Wu, Y. J. Mater. Chem. 2012, 22,
3201.
(18) (a) Xie, Z.; Ma, L.; DeKrafft, K. E.; Jin, A.; Lin, W. J. Am. Chem.
Soc. 2010, 132, 922. (b) Lan, A.; Li, K.; Wu, H.; Olson, D. H.; Emge,
T. J.; Ki, W.; Hong, M.; Li, J. Angew. Chem., Int. Ed. 2009, 48, 2334.
(c) Cui, J. H.; Lu, Z. Z.; Li, Y. Z.; Guo, Z. J.; Zheng, H. G. Chem.
Commun. 2012, 48, 7967. (d) Wang, J. H.; Li, M.; Li, D. Chem. Sci.
2013, 4, 1793. (e) Dang, S.; Min, X.; Yang, W.; Yi, F. Y.; You, H.; Sun,
Z. M. Chem.Eur. J. 2013, 19, 17172.
ACKNOWLEDGMENTS
■
This work was supported by grants from the Natural Science
Foundation of China (nos. 91022011, 21021062, 20971065,
and 21371092) and the National Basic Research Program of
China (no. 2010CB923303).
DEDICATION
■
Dedicated to Professor Xin-Quan Xin on the occasion of his
80th birthday.
REFERENCES
■
(1) (a) Kong, X. Q.; Deng, H. X.; Yan, F. Y.; Kim, J.; Swisher, J. A.;
Smit, B.; Yaghi, O. M.; Reimer, J. A. Science 2013, 341, 882. (b) Duan,
J. G.; Higuchi, M.; Foo, M. L.; Horike, S.; Rao, K. P.; Kitagawa, S.
Inorg. Chem. 2013, 52, 8244. (c) Deng, H. X.; Grunder, S.; Cordova, K.
́
E.; Valente, C.; Furukawa, H.; Hmadeh, M.; Gandara, F.; Whalley, A.
C.; Liu, Z.; Asahina, S.; Kazumori, H.; O′Keeffe, M.; Terasaki, O.;
Stoddart, J. F.; Yaghi, O. M. Science 2012, 336, 1018.
(2) (a) Wriedt, M.; Yakovenko, A. A.; Halder, G. J.; Prosvirin, A. V.;
Dunbar, K. R.; Zhou, H. C. J. Am. Chem. Soc. 2013, 135, 4040.
(b) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.;
Forrest, K.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.;
Zaworotko, M. J. Nature 2013, 495, 80. (c) Yang, Q. X.; Chen, Z. J.;
Hu, J. S.; Hao, Y.; Li, Y. Z.; Lu, Q. Y.; Zheng, H. G. Chem. Commun.
2013, 49, 3585. (d) Wang, C.; Wang, J. L.; Lin, W. B. J. Am. Chem. Soc.
2012, 134, 19895.
(3) (a) Fairen-Jimenez, D.; Moggach, S. A.; Wharmby, M. T.; Wright,
P. A.; Parsons, S.; Duren, T. J. Am. Chem. Soc. 2011, 133, 8900.
̈
(b) Ma, S. Q.; Sun, D. F.; Yuan, D. Q.; Wang, X. S.; Zhou, H. C. J. Am.
Chem. Soc. 2009, 131, 6445.
(4) Ma, S. Q.; Yuan, D. Q.; Wang, X. S.; Zhou, H. C. Inorg. Chem.
2009, 48, 2072.
2746
dx.doi.org/10.1021/cg500269h | Cryst. Growth Des. 2014, 14, 2742−2746