ARTICLE pubs.acs.org/crystal
Two Porous Zinc Coordination Polymers with (10,3) Topological Features Based on a N-Centered Tripodal Ligand and the Conversion of a (10,3)-d Subnet to a (10,3)-a Subnet Xiao-Qiang Yao,† Ming-Dao Zhang,† Jin-Song Hu,† Yi-Zhi Li,† Zi-Jian Guo,† and He-Gen Zheng*,†,‡ †
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China ‡ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China
bS Supporting Information ABSTRACT: Two porous (3,4)-connected zinc coordination polymers, {[Zn(TIPA)(mal)1/2](NO3) 3 3H2O}n (1) and {[Zn(TIPA)(glu)1/2](NO3) 3 H2O}n (2) (mal = malonic acid, glu = glutaric acid, TIPA = tris(4-(1H-imidazol-1-yl)phenyl)amine) have been hydrothermally synthesized and characterized. Complex 1 crystallizes in the orthorhombic space group Pnna (No. 52) containing an unusual 3D subnet with (10,3)-d topology and leftand right-handed helical channels. Complex 2 crystallizes in the orthorhombic chiral space group P2221 (No. 17) containing an unusual 3D chiral subnet with (10,3)-a topology and 4-fold righthanded helical channels. The conversion of achiral complex 1 with a (10,3)-d (utp) achiral subnet to chiral complex 2 with a (10,3)-a (srs) chiral subnet has been successfully induced by increasing the length of ditopic aliphatic dicarboxylic acid. Second harmonic generation (SHG) measurement was performed on complex 2 revealing that 2 has a strong SHG response, and the SHG efficiency is approximately 0.8 times that of urea (ca. 8 times that of KDP). In addition, photoluminescence and thermogravimetric analysis were also performed on 1 and 2.
’ INTRODUCTION Metalorganic frameworks (MOFs) have attracted much attention for their potential application in gas storage, in carbon dioxide capture, as renewable catalysts, and in drug delivery.14 In recent years, chiral metalorganic frameworks with helical channels have been of particular interest and importance because of their unique properties for applications such as asymmetric catalysis, chiral separations, and second-harmonic generation (SHG).5 The traditional method to synthesize metalorganic open-framework materials with chiral features is the use of a chiral additive or structure-directing agent; the chirality of these additives can be transferred to the inorganicorganic hybrid framework.6 Compared with the chiral induction approach, the induction of chiral porous solids containing only achiral building blocks is a new promising direction.7 Possessing either large channels or chirality that is the intrinsic characteristic of (10,3) topological metalorganic frameworks, their chirality commonly derives from the spatial organization (e.g., helix) of achiral components rather than chiral additives.8 One of the effective approaches is to choose triangular organic ligands as the triangular nodes or trichelated metal complexes as trigonal building blocks.9 Though some related synthetic strategy in constructing the € (10,3) topological MOFs has been summarized by Ohrstr€ om,10 a systematic synthetic procedure for synthesizing such (10,3)-type r 2011 American Chemical Society
complexes has not yet been done. In this work, we introduce a feasible strategy to synthesize such porous metalorganic frameworks possessing (10,3) topology based on Zn2+ and mixed ligands of a N-centered extended tripodal (ligand tris(4-(1H-imidazol-1-yl)phenyl)amine, TIPA) and two flexible aliphatic carboxylic acids (malonic acid and glutaric acid). Through this procedure, two novel zinc coordination polymers containing two unusual ZnTIPA substructures (ZnTIPA#1 in 1 and ZnTIPA#2 in 2) with (10,3)-d and (10,3)-a topology have been successfully synthesized. Both 1 and 2 feature (3,4)-connected noninterpenetrated 3D frameworks. If the mal and glu ligands are neglected from the structures, two 2-fold interpenetrated (10,3) topological networks can be observed. As is well-known, interpenetration can enhance stability of MOFs;11 the incorporation of mal and glu ligands further reinforce the stability of 1 and 2. To the best of our knowledge, so far, just one example related to (10,3)-d Zn-SIP subnet (SIP = 5-sulfoisophthalate) has been reported recently;12 however, in this example, the channels are almost fully occupied by 1,3-di-4-pyridylpropane (DPP) ligands. It is noteworthy that the mal and glu ligands have only trivial negative effect on the total void value of the Received: March 14, 2011 Revised: May 17, 2011 Published: May 31, 2011 3039
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Crystal Growth & Design channels in 1 and 2. Besides, the complex 2 containing a chiral (10,3)-a net as a subunit is yet to be reported. Not only that, it is also the first example demonstrating the conversion of the achiral (10,3)d (utp) net to chiral (10,3)-a (srs) net.
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Table 1. Crystallographic Data and Structure Refinement Details for complexes 1 and 2 complex formula
1 2 C57H56N16O16Zn2 C59H52N16O12Zn2
’ EXPERIMENTAL SECTION
formula weight
1351.92
1343.94
crystal system
orthorhombic
orthorhombic
Materials and Methods. The triangular ligand TIPA was synthesized according to the literature.13 All other reagents and solvents were commercially purchased without further purification. The IR absorption spectra of the complexes were recorded in the range of 4004000 cm1 by means of a Nicolet (Impact 410) spectrometer with KBr pellets (5 mg of sample in 500 mg of KBr). C, H, and N analyses were carried out with a Perkin-Elmer 240C elemental analyzer. XRD measurements were performed on a Bruker D8 Advance X-ray diffractometer using Cu KR radiation (1.5418 Å), in which the X-ray tube was operated at 40 kV and 40 mA. Luminescence spectra for the solid samples were recorded on an AMINCO Bowman series 2 fluorescence spectrophotometer at room temperature (25 °C). The emission decay lifetimes were measured on an Edinburgh Instruments FLS920 fluorescence spectrometer. A pulsed Q-switched Nd: YAG laser at a wavelength of 1064 nm was used to generate the SHG signal.14 The backward-scattered SHG light was collected by a spherical concave mirror and passed through a filter that transmits only 532 nm radiation. Thermogravimetric analysis (TGA) data were recorded by a simultaneous SDT 2960 thermal analyzer from 25 to 750 °C with a heating rate of 10 °C min1 in N2 atmosphere (a flow rate of 100 mL min1). Synthesis of {[Zn(TIPA)(mal)1/2](NO3) 3 3H2O}n (1). A solvothermal reaction of Zn(NO3)2 (0.076 g, 0.40 mmol), TIPA (0.088 g, 0.20 mmol), and malonic acid (0.021 g, 0.20 mmol) was conducted in the mixed solvents of DMF and H2O (v/v = 1:2) in a Teflon-lined stainless steel vessel and heated at 90 °C for three days, and the mixture was then cooled to room temperature. The colorless bulky crystals of 1 were obtained in high yield (90% based on TIPA ligand). Anal. Calcd for C57H56N16O16Zn2: C, 50.64; H, 4.18; N, 16.58%. Found: C, 50.87; H, 4.61; N, 16.71%. IR (KBr, cm1): 3411m, 3113w, 1662s, 1604m, 1519s, 1358m, 1313m, 1262w, 1125m, 1064m, 960w, 831m, 751w, 653m, 545w, 444w. Synthesis of {[Zn(TIPA)(glu)1/2](NO3) 3 H2O}n (2). A solvothermal reaction of Zn(NO3)2 (0.085 g, 0.41 mmol), TIPA (0.105 g, 0.23 mmol), and glutaric acid (0.028 g, 0.20 mmol) was conducted in the mixed solvents of DEF (N,N0 -diethylformamide) and H2O (v/v = 1:4) in a Teflon-lined stainless steel vessel and heated at 120 °C for three days, and the mixture was then cooled to room temperature. The yellow hexagonal prism crystals of 2 were obtained in 75% yield (based on TIPA ligand). Anal. Calcd for C59H52N16O12Zn2: C, 54.17; H, 4.01; N, 17.13%. Found: C, 54.43; H, 4.42; N, 17.33%. IR (KBr, cm1): 3417m, 3109w, 1659m, 1603m, 1518s, 1267m, 1122m, 1063m, 956w, 829m, 740w, 651w, 535w. X-ray Crystallography. X-ray crystallographic data of 1 and 2 were collected on a Bruker Apex Smart CCD diffractometer with graphite monochromatic Mo KR radiation (λ = 0.71073 Å). The structures of 1 and 2 were solved by direct methods, and the nonhydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using full-matrix least-squares procedures based on F2 values using the SHELXTL (version 6.14) package of crystallographic software.15 The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent atoms. The relevant crystallographic data are presented in Table 1, while the selected bond lengths and angles are given in Table S1 in the Supporting Information. The topological analysis and some diagrams were produced using the TOPOS program.16
space group
Pnna
P2221
a (Å)
28.330(3)
7.9114(11)
b (Å)
27.766(3)
14.2572(19)
c (Å) V (Å3)
9.9055(11) 7791.8(15)
29.557(4) 3333.8(8)
Z
4
2
Dc (g cm3)
1.153
1.303
μ(Mo KR) (mm1)
0.680
0.788
F(000)
2792
1348
θ min, max (deg)
1.6, 26.0
2.0, 26.0
total, unique data
40500, 7664
17988, 6530
R(int) obsd data [I > 2σ(I)]
0.076 4838
0.052 4922
Nref, Npar
7664, 444
6530, 435
R, wR2 [I > 2σ(I)]
0.0506, 0.1000
0.0675, 0.1325
S
1.01
’ RESULTS AND DISCUSSION Descriptions of Crystal Structures. Complex 1 crystallizes in the orthorhombic space group Pnna. The asymmetric unit of 1
absolute structure parameter
0.028(19)
min, max residual density (e 3 Å3) 0.31, 0.37
1.08 0.73, 0.51
R1 = ∑||Fo| |Fc||/∑|Fo|; wR2 = {∑[w(Fo2 Fc2)2]/ ∑[w(Fo2)2]}1/2 where w = 1/[σ2(Fo2) + (aP)2 + bP], P = (Fo2 + 2Fc2)/3.
Figure 1. ORTEP drawing of the molecular structure of 1 with 30% probability thermal ellipsoids. Symmetry codes: A = 0.5 + x, y, z; B = 0.5 x, 1 y, z; C = 1 x, 0.5 + y, 0.5 + z.
consists of one Zn2+ ion, one TIPA ligand, half a mal2 ligand, eight disordered water molecules, and one noncoordinated nitrate anion. As depicted in Figure 1, the Zn1 atom is four-coordinated by three N atoms from three individual TIPA ligands and one O atom from one carboxylate group of mal2 ligand in a somewhat distorted tetrahedral geometry. The mal2 ligand adopts a bidentate bridging coordination mode through its monodentate carboxylate group; the Zn 3 3 3 Zn distances through the mal2 ligands are 6.75 Å. The Zn2+ ions are connected by TIPA and mal2 ligands to form a complicated 3D network with a hexagonal helical channel along the c axis, 3040
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Figure 2. (a) Three-dimensional 2-fold interpenetrated ZnTIPA#1 framework of 1 view down the c axis, showing the left- and right-handed (L/R) helical channels. (b) Left- and right-handed double homochiral helical chains in 1.
as shown in Figure S1a in the Supporting Information. The total void value of the channels without water guests and noncoordinated nitrate anions is estimated (by Platon17) to be 3262.6 Å3, approximately 41.9% of the total crystal volume, 7791.8 Å3. Water molecules are accommodated in a disordered fashion in the channels (Supporting Information, Figures S1c). A better insight into the nature of this complicated architecture can be achieved if the mal2 ligands are neglected from the structure. Elimination of the mal2 ligands leaves a 2-fold interpenetrated 3D ZnTIPA#1 substructure with hexagonal helical channels along the c axis (Figure 2a). As illustrated in Figure 2b, the Zn2+ ions are linked up by TIPA ligands to give rise to two types of helical chains with opposite chirality. Each channel consists of left- or right-handed double homochiral helical chains. Because the right- and left-handed double homochiral helices are alternately arranged, the whole chirality of the ZnTIPA#1 subnet is therefore racemic. The dimensions of the hexagonal helical channels are approximately 11.31 10.06 Å2. In this ZnTIPA#1 subnetwork, the Zn2+ ion is linked to three individual TIPA ligands, and each TIPA ligand links three Zn2+ ions. Both Zn2+ ions and TIPA ligands can be treated as 3-connected nodes. Topologically, the ZnTIPA#1 subnetwork can thus be simplified to a (3,3)-connected network; these two three-connected nodes are topologically equivalent nodes. As determined by TOPOS software, the Schl€afli symbol for this (3,3)-connected binodal network is 103, which is assigned to the (10,3)-d, utp topology. A single ZnTIPA#1 subnet of 1 closely resembles the ideal (10,3)-d net, which is constructed by the alternately arranged right- and left-handed hexagonal helices along the c axis (Figure 3). Each hexagonal helix connects to six adjacent helices by sharing a common edge, which projects as a (6,3) net (along the ab plane). To the best of our knowledge, just one recently reported zinc carboxylatesulfonate substructure with (10,3)-d topology has been known to be present in coordination polymers. However, in this example, the channels are almost fully occupied by 1,3-di-4-pyridylpropane (DPP) ligands. In contrast, the mal ligands have only trivial negative effect on the total void value of the channels in 1. In the structure of 1, the mal2 ligands join up Zn2+ cations of the 2-fold interpenetrated ZnTIPA#1 substructures to form a (3,4)-connected noninterpenetrated 3D network (Figure S1b in the Supporting Information). The incipient voids of 1 contain a solvent-accessible void space of 41.9% of the total crystal volume. To evaluate the negative effect of mal2 on void space of 1, the mal ligands are subtracted from complex 1. The total void value of the channels without water molecules and noncoordinated nitrate anions slightly increases from 3262.6 to 3610.7 Å3, approximately 46.3% of
Figure 3. Schematic representation of the (10,3)-d subnet in 1 along the c axis (the turquoise and blue balls represent the Zn atoms and TIPA ligands, respectively). One 10-membered shortest circuit and a single helix are highlighted by violet and pink, respectively.
the total crystal volume. This suggests that the incorporation of flexible aliphatic carboxylate anions just slightly reduces the volume of the channels. Moreover, the incorporation of mal2 to ZnTIPA#1 substructure enhances the yield and the stability of 1, which can be stable for several days when it is exposed to air. By comparison, the complex assembled directly from Zn2+ and TIPA ligand is unstable in air, though it has the same structure with the ZnTIPA#1 substructure of complex 1. In addition, it is hard to obtain by a similar synthetic procedure for 1. Despite its poor crystal quality and low yield, we still determined its cell parameters of a = 28.368, b = 28.368(13), c = 9.408(4) Å, and R = β = γ = 90°, it also crystallizes in the orthorhombic space group Pnna. It is notable that the crystal expands in the a and b direction from 27.776(3) and 28.330(3) Å to 28.368 and 28.368(13) Å but shrinks in the c direction from 9.906(1) to 9.408(4) Å in comparison with 1. Complex 2 crystallizes in the orthorhombic chiral space group P2221. The asymmetric unit of 2 consists of one Zn2+ cation, one TIPA ligand, half a glu2 ligand, one noncoordinated nitrate anion, which is disordered over two positions, and one water molecule, which is distributed fractionally over three positions. As depicted in Figure 4, the Zn1 atom is five-coordinated by three N atoms from three individual TIPA ligands and two O atoms from one carboxylate group of glu2 ligand in a distorted tetragonal pyramid geometry. The coordination environment of complex 2 is similar to that of 1, except that each glu2 ligand with antianti conformation adopts a bidentate bridging coordination mode to connect two Zn2+ cations together through its bidentate carboxylate group. The Zn 3 3 3 Zn distance through the glu2 ligands is 9.75 Å. 3041
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Figure 4. ORTEP drawing of the molecular structure of 2 with 30% probability thermal ellipsoids. Symmetry codes: A = x, y, 0.5 z; B = 1 x, 1 y, 0.5 + z; C = 1 + x, 2 y, 1 z.
Figure 5. (a) Three-dimensional 2-fold interpenetrated ZnTIPA#2 framework in 2 view down the a axis, (b) 2-fold interpenetrated (10,3)-a net of ZnTIPA#2, and (c) two independent identical (10,3)-a components of ZnTIPA#2 subnet of 2 along the a axis (the turquoise and blue balls represent the Zn atoms and TIPA ligands, respectively). One 10membered shortest circuit is highlighted by violet.
The same method used for 1 was employed to analyze the structure of 2. Elimination of the glu2 ligand also leaves a 2-fold interpenetrated 3D ZnTIPA#2 substructure, which is quite different from the ZnTIPA#1 substructure in complex 1. As illustrated in Figure 5a, in the ZnTIPA#2 subnetwork, the Zn2+ cations are interconnected by TIPA ligands to form a 2-fold interpenetrated 3D architecture with 4-fold helical channels along the a axis, both Zn2+ cations and TIPA ligands can be treated as three-connected nodes. The overall topology of ZnTIPA#2 substructure is a (3,3)-connected 2-fold interpenetrating network (Figure 5b). As determined by TOPOS software, the Schl€afli symbol for this (3,3)-connected binodal network is 103 and is assigned to the (10,3)-a, srs net (Figure 5c). The main feature of this (10,3)-a
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Figure 6. The scheme demonstrates the evolution from (10,3)-d Zn TIPA#1 subnet (left) in 1 to (10,3)-a ZnTIPA#2 subnet (right) in 2, achieved by increasing the length of flexible aliphatic dicarboxylic acid.
net is 4-fold helices extending along all axes. The helices are of the same handedness. In the ZnTIPA#2 subnet of 2, the helices are all homochiral right-handed. To the best of our knowledge, such a (10,3)-a net as a subunit of a coordination polymer has not been reported previously. As illustrated by Figure S2a,b in the Supporting Information, the glu2 ligands further link Zn2+ cations of the 2-fold interpenetrated ZnTIPA#2 substructures to form a (3,4)-connected noninterpenetrated 3D network. Considering the coordination framework alone, the total void is estimated to be 906.9 Å3, approximately 27.2% of the total crystal volume 3333.9 Å3. To investigate the negative effect of glu ligands on the void space, the glu ligands are subtracted from complex 2. The total void value of the channels without water molecules and noncoordinated nitrate anions just slightly increases to 1062.1 Å3, approximately 31.9% of the total crystal volume. The Conversion of the (10,3)-d Subnet to the (10,3)-a Subnet. The ZnTIPA#1 subnet of complex 1 is a 2-fold interpenetrated (10,3)-d network with utp topology. We have discussed the effect of the mal2 ligand on the structure of 1 in the preceding paper. The significant role of mal2 in 1 suggested that some other coordination polymer with (10,3) subnet may be obtained by increasing the length of the flexible aliphatic dicarboxylic acid. As to be expected, when we replace the malonic acid with glutaric acid, a chiral porous zinc coordination polymer (complex 2) containing a ZnTIPA#2 substructure with (10,3)-a, srs topology has been successfully synthesized. The ZnTIPA#1 substructure and the ZnTIPA#2 substructure are structural isomers. Though the coordination environment of 2 is a slightly different from that of 1, the structures of these two substructures are quite different. The distinct structural deviation between ZnTIPA#1 and ZnTIPA#2 substructures may originate from the template effect of mal2 and glu2 ligands. In these two substructures, each Zn2+ ion connects three N atoms of different TIPA ligands to form a tetrahedral node Zn(TIPA)3 as a building block, leading to the formation of (3,3)connected frameworks. We define the plane consisting of three N atoms as the basal plane of tetrahedral node Zn(TIPA)3. As depicted in Figure 6, when the mal2 ligands are replaced by glu2 ligands, the Zn 3 3 3 Zn distance in 2 increases to 9.75 from 6.75 Å in 1, and the dihedral angle of basal planes of two adjacent tetrahedral nodes decreases to 43.67° from 85.16°. As a result, the ZnTIPA#1 subnet with (10,3)-d topology transforms into ZnTIPA#2 subnet with (10,3)-a topology. Luminescent Properties. Considering that d10 metal complexes usually exhibit excellent luminescent properties, the 3042
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Figure 7. Photoluminescence spectra of 1, 2, and TIPA ligand in the solid state at room temperature.
photoluminescence properties of 1 and 2 were investigated in the solid state at room temperature (Figure 7). Complex 1 exhibits an intense photoluminescent peak with a maximum at 403 nm upon excitation at 354 nm, and complex 2 exhibits an intense emission with a maximum at 398 nm upon excitation at 367 nm. To understand the nature of the emission spectra, the luminescence properties of the free TIPA ligands and the two flexible aliphatic carboxylic acids under the same experimental conditions were recorded for comparison. An intense emission of the free TIPA ligand is observed with wavelength from 374 to 490 nm (λmax = 405 nm upon excitation at 388 nm). Both mal and glu ligands show no observable fluorescence. The emission peaks of 1 and 2 are essentially the same as the photoluminescent peak of TIPA, which indicates that the emission bands of 1 and 2 are intraligand transitions (LLCT). The two emission bands can be ascribed to ππ* or πn transitions within the molecular orbital manifolds of imidazolyl and phenyl rings of TIPA moieties. In comparison with the free TIPA ligand, 1 and 2 show slightly blue-shifted emission bands, and the fluorescence intensities are obviously decreased. On the one hand, the blue shifts of 1 and 2 may be presumably a result of the increase of the rigidity and asymmetry of the ligands; on the other hand, the decrease in intensity of the fluorescence may result from the collisions of water molecules in the channel.18 When the solvent water molecules in channels of 1 and 2 are removed, the fluorescence intensity of dried 1 is ∼4.5 times higher compared with pristine 1 and the fluorescence intensity of dried 2 also shows a distinct enhancement compared with pristine 2. In addition, the emission decay lifetimes of dehydrated complexes 1 and 2 were monitored, and the curves are best fit by biexponentials in the solid.19 The emission decay lifetimes of the dehydrated complexes 1 and 2 are as follows: dehydrated complex 1, τ1 = 0.37 ns (48.17%) and τ2 = 3.15 ns (51.83%) (χ2 = 1.230, Supporting Information, Figure S4); dehydrated complex 2, τ1 = 0.58 ns (57.38%) and τ2 = 2.90 ns (42.62%) (χ2 = 1.107, Supporting Information, Figure S5). Thermal Analysis and XRPD Results. Complexes 1 and 2 are air-stable and insoluble in water and common organic solvents such as methanol, ethanol, acetonitrile, acetone, DMF, and chloroform. The thermogravimetric analysis (TGA) was performed in N2 atmosphere on polycrystalline samples of complexes
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1 and 2, and the TG curves are shown in Figure S3 in the Supporting Information. The TG curve of 1 shows the first weight loss of 11.80% in the temperature range 20119 °C, which corresponds to the loss of the three lattice water molecules; then, its weight is stable up to 190 °C, at which the framework begins to collapse. For 2, the solvate loss (6.02%) occurs in the temperature range 22120 °C, which corresponds to the loss of the lattice water molecules. The framework of 2 remains intact up to 277 °C, at which the framework begins to collapse. The purity of complexes 1 and 2 is confirmed by powder XRD analyses, in which the main peaks of experimental spectra of 1 and 2 are basically consistent with their simulated spectra. To investigate the stability of 1 and 2 when the solvent water molecules were removed from channels, the crystals of 1 and 2 were soaked in methylene dichloride (CH2Cl2) three times for 12 h at a time and then dried under vacuum at 60 °C. The powder X-ray diffraction pattern of the vacuum-dried samples of 1 and 2 shows the structure still retained (Supporting Information, Figures S6 and S7). Powder Second Harmonic Generation Results. Considering that complex 2 crystallizes in the chiral space group P2221, its nonlinear optical properties were studied. Second harmonic generation (SHG) measurements on powder samples using 1064 nm radiation were performed on complex 2 and revealed that the material has a strong SHG response and the SHG efficiency is approximately 0.8 times that of urea (ca. 8 times that of KDP), which evaluates its potential as a second-order nonlinear optical material.
’ CONCLUSION In summary, we have synthesized two porous zinc coordination polymers containing (10,3) subnets constructed by Zn2+ and TIPA ligand and demonstrated the conversion of a (10,3)-d achiral net to a chiral (10,3)-a net by increasing the length of flexible aliphatic dicarboxylic acid. In this work, the use of flexible aliphatic carboxylic acid to construct (10,3)-topological MOFs has been proven to be feasible. We believe that some other MOFs with (10,3) characteristics can be constructed by this synthetic strategy. Complex 2 shows a strong SHG response. In addition, 1 and 2 display modest thermal stability and strong solid-state fluorescent emission. ’ ASSOCIATED CONTENT
bS
Supporting Information. Crystallographic data in CIF format, selected bond lengths and angles, TGA, and PXRD. This material is available free of charge via the Internet at http:// pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. Fax: 86-25-83314502.
’ ACKNOWLEDGMENT This work was supported by grants from the Natural Science Foundation of China (Nos. 20971065, 91022011, and 21021062) and National Basic Research Program of China (Nos. 2010CB923303 and 2007CB925103). 3043
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Crystal Growth & Design
ARTICLE
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dx.doi.org/10.1021/cg200315f |Cryst. Growth Des. 2011, 11, 3039–3044
