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Zigzag on a zigzag: Trap of hydrogen-bonded water molecules in a luminescent metal–organic network
Inorganic Chemistry Communications 9 (2006) 1243–1246 www.elsevier.com/locate/inoche
Zigzag on a zigzag: Trap of hydrogen-bonded water molecules in a luminescent metal–organic network Kunlin Huang a
a,b
, Yanting He a, Xueli Niu a, Xiangyu Chen a, Yingnan Chi a, Yun Gong a, Changwen Hu a,*
Department of Chemistry and The Institute for Chemical Physics, Beijing Institute of Technology, Beijing 100081, China b College of Chemistry, Chongqing Normal University, Chongqing 400047, China Received 8 June 2006; accepted 30 July 2006 Available online 11 August 2006
Abstract A four-connected 2-D metal–organic coordination polymer {[Cd(mpdc)(phen)] Æ H2O}(mpdc = 2,6-dimethylpyridine-3,5-dicarboxylate, phen = 1,10-phenanthroline) has been assemblied from cadmium ions and two kinds of organic ligands under hydrothermal conditions, characterized by single-crystal X-ray diffraction analysis. The 2-D metal–organic network was constructed from binuclear [Cd(O5N2)]2 clusters bridged by mpdc2 ligands. The most interesting is that water molecules trapped by the 2-D network look as if its motif is projected from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions. In addition, new compound exhibits strong luminescence at kmax = 525 nm upon excitation at 367 nm. 2006 Elsevier B.V. All rights reserved. Keywords: Cadmium; Carboxylate; Coordination polymer; Hydrothermal reaction; Luminescence
Current interest in metal–organic frameworks (MOFs) is rapidly expanding for their potential applications and intriguing structural features [1], although the prediction and synthesis of the solid-state architectures still remains a long-term challenge for the chemists [2]. In the past few decades, the development of supramolecular assembled chemistry has allowed the possibility to rationally design and prepare supramolecular architectures [3]. Most studies show that the combination of metal coordination and supramolecular interaction (hydrogen bonding and p–p stacking) is a powerful force for supramolecular structural assembly in crystal engineering [4]. Compared with benzene dicarboxylic acid, pyridine dicarboxylic acid has advantages over the former such as having rich coordination modes, being the hydrogen-bond donors and acceptors [1,5]. Pyridine dicarboxylic acids are therefore regarded as excellent candidates for the construc*
Corresponding author. Tel./fax: +86 10 62828869. E-mail address: [email protected] (C. Hu).
1387-7003/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.07.042
tion of MOFs, for example, pyridine-2,6-dicarboxylates, pyridine-2,5-dicarboxylates and pyridine-3,5-dicarboxylates (Scheme 1). Although one could anticipate that substituted pyridine-3,5-dicarboxylic acids will be applied as versatile ligand as pyridine-3,5-dicarboxylic acid in the construction of functional MOFs, their coordination chemistry has not been explored until now [6]. Our interest focuses on the substituted PDC for the self-assemblies of metal–organic coordination and supramolecular architectures. For well-known electron donor, alkyl groups could make for the red shift of luminescence (close to visible light). Here, we report a luminescent 2-D metal–organic network {[Cd(mpdc)(phen)] Æ H2O} (1, mpdc = 2,6dimethyl pyridine-3,5-dicarboxylate) with trapped H2O molecules arranged in zigzag motif which looks as if is projected from the zigzag arrangement of cadmium atoms in the 2-D network. The colorless crystalline compound 1 is synthesized by treating Cd(NO3)2 with H2mpdc (mpdc = 2,6-dimethylpyridine-3,5-dicarboxylate) and 1,10-phenanthroline
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K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246 -
-
O2C
-
O2C
N
CO2-
2, 6-PDC
O2C
N CO 22, 5-PDC
CO2-
N 3, 5-PDC
-
CO2-
O2C N mpdc
Scheme 1.
(phen) in the molar ratio of 1:1:1 in a solution of H2O and triethylamine at pH 6 and 140 C [7]. X-ray diffraction analysis reveal that 1 crystallizes in the space group P21/c [8]. The crystal structure reveals that compound 1 consists of a neutral {[Cd(mpdc)(phen)] Æ H2O}. This material is stable in air and is insoluble in common organic solvents such as methanol, ethanol, acetonitrile, acetone, and DMF. The formulation of 1 is supported by FT-IR, microanalysis, and thermogravimetric analysis (TGA). The X-ray power diffraction pattern proves the sample is pure-phase. In the structure of 1, the cadmium center adopts sevencoordinated mode with a distorted pentagonal bipyramid or decahedron (CdO5N2) via binding to two nitrogen atoms (N2, N3) from phen ligands and five oxygen atoms (O1, O2; O3, O4; O3A) originating from different carboxylate groups of mpdc2 ligands. Thus two mpdc2 ligands link two cadmium atoms to form a binuclear [Cd(O5N2)]2 cluster (Fig. 1). The Cd–O bond lengths are in the ranges ˚ and Cd1–N bond lengths are 2.377 and of 2.286–2.671 A ˚ 2.381 A, which are similar to those observed in [Cd(bpea)(phen)2] [9], [Cd(2-PEB)2 Æ H2O] [10], Cd(2-CEQA)(Py), [10] {[Cd(o-O2CC6H4COFc)2(bpe)(MeOH)2] Æ H2O} [11], and cadmium (4-pyridyl)acrylate [12].
Fig. 1. Thermal ellipsoid (50%) plot of: (a) binuclear cluster [Cd(O5N2)]2 of compound 1; (b) the structural building unit composed of {[Cd4(mpdc)4] Æ 2H2O} displays a 32-membered ring hosting two water ˚ ]: Cd(1)–O(3A), 2.286(2); molecules. Selected interatomic distances [A Cd(1)–O(1), 2.301(2); Cd(1)–O(4), 2.319(2); Cd(1)–N(3), 2.376(3); Cd(1)– N(2), 2.380(3); Cd(1)–O(2), 2.434(2); Cd(1)–O(3), 2.671(2). Symmetric code: A x + 1, y + 1, z.
˚) The binuclear [Cd(O5N2)]2 clusters (Cd–Cd, 3.942 A 2 bridged by mpdc ligands give rise to a neutral fourconnected 2-D grid with a centrosymmetrical symmetry (Fig. 2a and Fig. S1). Four-membered ring constructed from four binuclear [Cd(O5N2)]2 clusters and four mpdc2 ligands traps two H2O molecules by hydrogen bonds ˚ and O5 O4 2.960 A ˚ ). We can see (O5 N1 2.894 A that the cadmium atoms in the 2-D network arrange in a zigzag motif. It is most interesting that this kind zigzag motif of cadmium atoms in the 2-D network apparently transfers its topological information to the trapped water molecules by hydrogen bonding interactions. So the water molecules trapped by the 2-D network through hydrogen bonds also exhibit an arrangement in a zigzag motif. The phenomenon is a novel example of information storage via hydrogen bonding interactions (Fig. 2b). Furthermore, a supramolecular 3-D framework can be built up from 2-D coordination polymeric grids via the p–p stacking of phen ˚ (Fig. 3). ligands with face-to-face distances of ca. 3.60 A Among the new luminescent cadmium-organic coordination compounds [13], Wang and co-workers [9] reported a remarkable metal polynuclear cluster {[Cd3(bpea)(phen)3(OH)3(H2O)] Æ 0.5bpea Æ 4H2O} with emission maximum at k = 489 nm. As expected, at room temperature, compound 1 shows strong photoluminescent emission maximum at k = 525 nm, which can be assigned to ligand– metal charge transfer (Fig. 4), while emission maximums
Fig. 2. (a) View of the four-connected 2-D coordination polymer with binuclear [Cd(O5N2)]2 clusters as nodes highlighted with polyhedron mode. (b) The H2O molecules trapped by the 2-D network arranged in a zigzag motif ‘‘projected’’ out from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions (view along from [0 0 1] direction).
K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246
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Fig. 3. View of the supramolecular 3-D framework constructed from 4-connected 2-D coordination polymeric grid by p–p stacking interactions.
of free H2mpdc and phen ligands are at 472 and 425 nm, respectively, upon excitation at k = 367 nm. Emission maximum with obvious red-shift might make 1 a potentially useful photoactive solid-state material for its thermal and chemical stability [14]. In conclusion, by taking advantage of simple modifications of pyridine-3,5-dicarboxylates, we successfully employed the mpdc2 ligands as V-shaped spacers in the assembly of 2-D metal–organic network {[Cd(mpdc)(phen)] Æ H2O} (1) with binuclear [Cd(O5N2)]2 clusters. The water molecules trapped by the 2-D network arranged in zigzag motif look as if its motif is projected from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions. The supramolecular 3-D framework can be constructed from four-connected 2-D coordination polymeric grids by p–p stacking interactions. Compound 1 exhibits expected luminescence at kmax = 525 nm upon excitation at 367 nm.
Fig. 4. Emission spectra of (a) H2mpdc ligand (kmax = 472 nm) and (b) 1 (kmax = 525 nm), upon excitation at 367 nm.
Acknowledgements This work was supported by the National Natural Science Foundation of China (Nos. 20331010 and 90406002), Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20030007014) and Science Foundation of Chongqing Municipal Education Commission (No. KJ060802). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.inoche.2006.07.042. References [1] (a) G. Fe´rey, C. Mellot-draznieks, C. Serre, F. Millange, Acc. Chem. Res. 38 (2005) 217; (b) J.L.C. Rowsell, O.M. Yaghi, Angew. Chem., Int. Ed. 44 (2005) 4670; (c) S.J. Loeb, Chem. Commun. (2005) 1511; (d) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334; (e) C.N.R. Rao, S. Natarajan, R. Vaidhyanthan, Angew. Chem., Int. Ed. 43 (2004) 1466; (f) O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaodi, J. Kim, Nature 423 (2003) 705; (g) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511; (h) O.M. Yaghi, H. Li, C. Davis, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474. [2] (a) N.W. Ockwig, O. Delgado-friedrichs, M. O’Keffe, O.M. Yaghi, Acc. Chem. Res. 38 (2005) 176; (b) O. Delgado-Friedrichs, M. O’Keeffe, J. Solid State Chem. 178 (2005) 2480; (c) L. Han, M. Hong, Inorg. Chem. Commun. 8 (2005) 406; (d) J.L.C. Rowsell, O.M. Yaghi, Micropor. Mesopor. Mater. 73 (2004) 3. [3] (a) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; (b) M.D. Ward, Chem. Commun. (2005) 5838; (c) A.M. Beatty, Coord. Chem. Rev. 246 (2003) 131; (d) J. Wang, S. Hu, M. Tong, Eur. J. Inorg. Chem. (2006) 2069.
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K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246
[4] B. Sreenivasulu, J.J. Vittal, Angew. Chem., Int. Ed. 43 (2004) 5769. [5] A. Erxleben, Coord. Chem. Rev. 246 (2003) 203. [6] (a) Y. Lu, J. Wu, M. Chan, S. Huang, C. Lin, T. Chiu, Y. Liu, Y. Wen, C. Ueng, T. Chin, C. Hung, K. Lu, Inorg. Chem. 45 (2006) 2430; (b) J.F. Eubank, R.D. Walsh, M. Eddaoudi, Chem. Commun. (2005) 2095. [7] A solution of H2O (10 mL) containing H2mpdc (0.2 mmol), 1,10phenanthroline (0.2 mmol), Cd(NO3)2 Æ 6H2O (0.2 mmol) and Et3N (0.04 mL) is sealed in a reactor of 23 mL and heated at 140 C for 72 h, then cooled at to room temperature. The colorless crystals are washed with ethanol (3 · 3 mL) to give compound 1 in yield of 60%. Element analysis for C42H34N6O10Cd2 (%), Calcd: C 50.02, H 3.37, N 8.33; found: C 50.13, H 3.24, N 8.19. IR (KBr): 3484m, 3230m, 3053w, 1591s, 1536m, 1428m, 1376s, 1151m, 860m, 730m, 681m. [8] Crystal data C42H34N6O10Cd2 (1),Mr = 1007.55, monoclinic, T = ˚ , b = 11.573(3) A ˚, 298(2) K, space group P21/c, a = 12.032(3) A ˚ , b = 104.552(4), V = 1976.1(9) A ˚ 3, Z = 2, q = c = 14.662(4) A 1.693 g cm 3, F(000) = 1008, GOF = 1.059. Of 10 090 total reflections collected, 3481 were unique (Rint = 0.0252). R = 0.0234 and wR = 0.0559 for 271 parameters and 2599 reflections [I > 2s(I)]. The structure is solved by direct methods and refined with a full-matrix
[9] [10] [11] [12] [13] [14]
least-squares technique based on F2 using the SHELXTL program package. All hydrogen atoms of water molecules, and non-hydrogen atoms are found from the Difference Fourier Map. CCDC-610193 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. X. Wang, C. Qin, E. Wang, L. Xu, Z. Su, C. Hu, Angew. Chem., Int. Ed. 43 (2004) 5036. J. Zhang, Y. Xie, Q. Ye, R. Xiong, Z. Xue, X. You, Eur. J. Inorg. Chem. (2003) 2572. G. Li, H. Hou, L. Li, X. Meng, Y. Fan, Y. Zhu, Inorg. Chem. 42 (2003) 4995. O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew. Chem., Int. Ed. 38 (1999) 536. X. Li, R. Cao, W. Bi, Y. Wang, Y. Wang, X. Li, Z. Guo, Cryst. Grown Des. 5 (2005) 1651, and refs. therein. The result of thermogravimetric analysis (TGA) for complex 1 measured under N2 displays the weight loss of 3.45% from 30 to 160 C corresponds to the loss of the free water molecules (calcd: 3.57%) and the framework decomposition in the temperature range of 340–700 C.
Zigzag on a zigzag: Trap of hydrogen-bonded water molecules in a luminescent metal–organic network Kunlin Huang a
a,b
, Yanting He a, Xueli Niu a, Xiangyu Chen a, Yingnan Chi a, Yun Gong a, Changwen Hu a,*
Department of Chemistry and The Institute for Chemical Physics, Beijing Institute of Technology, Beijing 100081, China b College of Chemistry, Chongqing Normal University, Chongqing 400047, China Received 8 June 2006; accepted 30 July 2006 Available online 11 August 2006
Abstract A four-connected 2-D metal–organic coordination polymer {[Cd(mpdc)(phen)] Æ H2O}(mpdc = 2,6-dimethylpyridine-3,5-dicarboxylate, phen = 1,10-phenanthroline) has been assemblied from cadmium ions and two kinds of organic ligands under hydrothermal conditions, characterized by single-crystal X-ray diffraction analysis. The 2-D metal–organic network was constructed from binuclear [Cd(O5N2)]2 clusters bridged by mpdc2 ligands. The most interesting is that water molecules trapped by the 2-D network look as if its motif is projected from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions. In addition, new compound exhibits strong luminescence at kmax = 525 nm upon excitation at 367 nm. 2006 Elsevier B.V. All rights reserved. Keywords: Cadmium; Carboxylate; Coordination polymer; Hydrothermal reaction; Luminescence
Current interest in metal–organic frameworks (MOFs) is rapidly expanding for their potential applications and intriguing structural features [1], although the prediction and synthesis of the solid-state architectures still remains a long-term challenge for the chemists [2]. In the past few decades, the development of supramolecular assembled chemistry has allowed the possibility to rationally design and prepare supramolecular architectures [3]. Most studies show that the combination of metal coordination and supramolecular interaction (hydrogen bonding and p–p stacking) is a powerful force for supramolecular structural assembly in crystal engineering [4]. Compared with benzene dicarboxylic acid, pyridine dicarboxylic acid has advantages over the former such as having rich coordination modes, being the hydrogen-bond donors and acceptors [1,5]. Pyridine dicarboxylic acids are therefore regarded as excellent candidates for the construc*
Corresponding author. Tel./fax: +86 10 62828869. E-mail address: [email protected] (C. Hu).
1387-7003/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.07.042
tion of MOFs, for example, pyridine-2,6-dicarboxylates, pyridine-2,5-dicarboxylates and pyridine-3,5-dicarboxylates (Scheme 1). Although one could anticipate that substituted pyridine-3,5-dicarboxylic acids will be applied as versatile ligand as pyridine-3,5-dicarboxylic acid in the construction of functional MOFs, their coordination chemistry has not been explored until now [6]. Our interest focuses on the substituted PDC for the self-assemblies of metal–organic coordination and supramolecular architectures. For well-known electron donor, alkyl groups could make for the red shift of luminescence (close to visible light). Here, we report a luminescent 2-D metal–organic network {[Cd(mpdc)(phen)] Æ H2O} (1, mpdc = 2,6dimethyl pyridine-3,5-dicarboxylate) with trapped H2O molecules arranged in zigzag motif which looks as if is projected from the zigzag arrangement of cadmium atoms in the 2-D network. The colorless crystalline compound 1 is synthesized by treating Cd(NO3)2 with H2mpdc (mpdc = 2,6-dimethylpyridine-3,5-dicarboxylate) and 1,10-phenanthroline
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K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246 -
-
O2C
-
O2C
N
CO2-
2, 6-PDC
O2C
N CO 22, 5-PDC
CO2-
N 3, 5-PDC
-
CO2-
O2C N mpdc
Scheme 1.
(phen) in the molar ratio of 1:1:1 in a solution of H2O and triethylamine at pH 6 and 140 C [7]. X-ray diffraction analysis reveal that 1 crystallizes in the space group P21/c [8]. The crystal structure reveals that compound 1 consists of a neutral {[Cd(mpdc)(phen)] Æ H2O}. This material is stable in air and is insoluble in common organic solvents such as methanol, ethanol, acetonitrile, acetone, and DMF. The formulation of 1 is supported by FT-IR, microanalysis, and thermogravimetric analysis (TGA). The X-ray power diffraction pattern proves the sample is pure-phase. In the structure of 1, the cadmium center adopts sevencoordinated mode with a distorted pentagonal bipyramid or decahedron (CdO5N2) via binding to two nitrogen atoms (N2, N3) from phen ligands and five oxygen atoms (O1, O2; O3, O4; O3A) originating from different carboxylate groups of mpdc2 ligands. Thus two mpdc2 ligands link two cadmium atoms to form a binuclear [Cd(O5N2)]2 cluster (Fig. 1). The Cd–O bond lengths are in the ranges ˚ and Cd1–N bond lengths are 2.377 and of 2.286–2.671 A ˚ 2.381 A, which are similar to those observed in [Cd(bpea)(phen)2] [9], [Cd(2-PEB)2 Æ H2O] [10], Cd(2-CEQA)(Py), [10] {[Cd(o-O2CC6H4COFc)2(bpe)(MeOH)2] Æ H2O} [11], and cadmium (4-pyridyl)acrylate [12].
Fig. 1. Thermal ellipsoid (50%) plot of: (a) binuclear cluster [Cd(O5N2)]2 of compound 1; (b) the structural building unit composed of {[Cd4(mpdc)4] Æ 2H2O} displays a 32-membered ring hosting two water ˚ ]: Cd(1)–O(3A), 2.286(2); molecules. Selected interatomic distances [A Cd(1)–O(1), 2.301(2); Cd(1)–O(4), 2.319(2); Cd(1)–N(3), 2.376(3); Cd(1)– N(2), 2.380(3); Cd(1)–O(2), 2.434(2); Cd(1)–O(3), 2.671(2). Symmetric code: A x + 1, y + 1, z.
˚) The binuclear [Cd(O5N2)]2 clusters (Cd–Cd, 3.942 A 2 bridged by mpdc ligands give rise to a neutral fourconnected 2-D grid with a centrosymmetrical symmetry (Fig. 2a and Fig. S1). Four-membered ring constructed from four binuclear [Cd(O5N2)]2 clusters and four mpdc2 ligands traps two H2O molecules by hydrogen bonds ˚ and O5 O4 2.960 A ˚ ). We can see (O5 N1 2.894 A that the cadmium atoms in the 2-D network arrange in a zigzag motif. It is most interesting that this kind zigzag motif of cadmium atoms in the 2-D network apparently transfers its topological information to the trapped water molecules by hydrogen bonding interactions. So the water molecules trapped by the 2-D network through hydrogen bonds also exhibit an arrangement in a zigzag motif. The phenomenon is a novel example of information storage via hydrogen bonding interactions (Fig. 2b). Furthermore, a supramolecular 3-D framework can be built up from 2-D coordination polymeric grids via the p–p stacking of phen ˚ (Fig. 3). ligands with face-to-face distances of ca. 3.60 A Among the new luminescent cadmium-organic coordination compounds [13], Wang and co-workers [9] reported a remarkable metal polynuclear cluster {[Cd3(bpea)(phen)3(OH)3(H2O)] Æ 0.5bpea Æ 4H2O} with emission maximum at k = 489 nm. As expected, at room temperature, compound 1 shows strong photoluminescent emission maximum at k = 525 nm, which can be assigned to ligand– metal charge transfer (Fig. 4), while emission maximums
Fig. 2. (a) View of the four-connected 2-D coordination polymer with binuclear [Cd(O5N2)]2 clusters as nodes highlighted with polyhedron mode. (b) The H2O molecules trapped by the 2-D network arranged in a zigzag motif ‘‘projected’’ out from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions (view along from [0 0 1] direction).
K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246
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Fig. 3. View of the supramolecular 3-D framework constructed from 4-connected 2-D coordination polymeric grid by p–p stacking interactions.
of free H2mpdc and phen ligands are at 472 and 425 nm, respectively, upon excitation at k = 367 nm. Emission maximum with obvious red-shift might make 1 a potentially useful photoactive solid-state material for its thermal and chemical stability [14]. In conclusion, by taking advantage of simple modifications of pyridine-3,5-dicarboxylates, we successfully employed the mpdc2 ligands as V-shaped spacers in the assembly of 2-D metal–organic network {[Cd(mpdc)(phen)] Æ H2O} (1) with binuclear [Cd(O5N2)]2 clusters. The water molecules trapped by the 2-D network arranged in zigzag motif look as if its motif is projected from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions. The supramolecular 3-D framework can be constructed from four-connected 2-D coordination polymeric grids by p–p stacking interactions. Compound 1 exhibits expected luminescence at kmax = 525 nm upon excitation at 367 nm.
Fig. 4. Emission spectra of (a) H2mpdc ligand (kmax = 472 nm) and (b) 1 (kmax = 525 nm), upon excitation at 367 nm.
Acknowledgements This work was supported by the National Natural Science Foundation of China (Nos. 20331010 and 90406002), Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20030007014) and Science Foundation of Chongqing Municipal Education Commission (No. KJ060802). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.inoche.2006.07.042. References [1] (a) G. Fe´rey, C. Mellot-draznieks, C. Serre, F. Millange, Acc. Chem. Res. 38 (2005) 217; (b) J.L.C. Rowsell, O.M. Yaghi, Angew. Chem., Int. Ed. 44 (2005) 4670; (c) S.J. Loeb, Chem. Commun. (2005) 1511; (d) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334; (e) C.N.R. Rao, S. Natarajan, R. Vaidhyanthan, Angew. Chem., Int. Ed. 43 (2004) 1466; (f) O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaodi, J. Kim, Nature 423 (2003) 705; (g) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511; (h) O.M. Yaghi, H. Li, C. Davis, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474. [2] (a) N.W. Ockwig, O. Delgado-friedrichs, M. O’Keffe, O.M. Yaghi, Acc. Chem. Res. 38 (2005) 176; (b) O. Delgado-Friedrichs, M. O’Keeffe, J. Solid State Chem. 178 (2005) 2480; (c) L. Han, M. Hong, Inorg. Chem. Commun. 8 (2005) 406; (d) J.L.C. Rowsell, O.M. Yaghi, Micropor. Mesopor. Mater. 73 (2004) 3. [3] (a) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; (b) M.D. Ward, Chem. Commun. (2005) 5838; (c) A.M. Beatty, Coord. Chem. Rev. 246 (2003) 131; (d) J. Wang, S. Hu, M. Tong, Eur. J. Inorg. Chem. (2006) 2069.
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K. Huang et al. / Inorganic Chemistry Communications 9 (2006) 1243–1246
[4] B. Sreenivasulu, J.J. Vittal, Angew. Chem., Int. Ed. 43 (2004) 5769. [5] A. Erxleben, Coord. Chem. Rev. 246 (2003) 203. [6] (a) Y. Lu, J. Wu, M. Chan, S. Huang, C. Lin, T. Chiu, Y. Liu, Y. Wen, C. Ueng, T. Chin, C. Hung, K. Lu, Inorg. Chem. 45 (2006) 2430; (b) J.F. Eubank, R.D. Walsh, M. Eddaoudi, Chem. Commun. (2005) 2095. [7] A solution of H2O (10 mL) containing H2mpdc (0.2 mmol), 1,10phenanthroline (0.2 mmol), Cd(NO3)2 Æ 6H2O (0.2 mmol) and Et3N (0.04 mL) is sealed in a reactor of 23 mL and heated at 140 C for 72 h, then cooled at to room temperature. The colorless crystals are washed with ethanol (3 · 3 mL) to give compound 1 in yield of 60%. Element analysis for C42H34N6O10Cd2 (%), Calcd: C 50.02, H 3.37, N 8.33; found: C 50.13, H 3.24, N 8.19. IR (KBr): 3484m, 3230m, 3053w, 1591s, 1536m, 1428m, 1376s, 1151m, 860m, 730m, 681m. [8] Crystal data C42H34N6O10Cd2 (1),Mr = 1007.55, monoclinic, T = ˚ , b = 11.573(3) A ˚, 298(2) K, space group P21/c, a = 12.032(3) A ˚ , b = 104.552(4), V = 1976.1(9) A ˚ 3, Z = 2, q = c = 14.662(4) A 1.693 g cm 3, F(000) = 1008, GOF = 1.059. Of 10 090 total reflections collected, 3481 were unique (Rint = 0.0252). R = 0.0234 and wR = 0.0559 for 271 parameters and 2599 reflections [I > 2s(I)]. The structure is solved by direct methods and refined with a full-matrix
[9] [10] [11] [12] [13] [14]
least-squares technique based on F2 using the SHELXTL program package. All hydrogen atoms of water molecules, and non-hydrogen atoms are found from the Difference Fourier Map. CCDC-610193 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. X. Wang, C. Qin, E. Wang, L. Xu, Z. Su, C. Hu, Angew. Chem., Int. Ed. 43 (2004) 5036. J. Zhang, Y. Xie, Q. Ye, R. Xiong, Z. Xue, X. You, Eur. J. Inorg. Chem. (2003) 2572. G. Li, H. Hou, L. Li, X. Meng, Y. Fan, Y. Zhu, Inorg. Chem. 42 (2003) 4995. O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew. Chem., Int. Ed. 38 (1999) 536. X. Li, R. Cao, W. Bi, Y. Wang, Y. Wang, X. Li, Z. Guo, Cryst. Grown Des. 5 (2005) 1651, and refs. therein. The result of thermogravimetric analysis (TGA) for complex 1 measured under N2 displays the weight loss of 3.45% from 30 to 160 C corresponds to the loss of the free water molecules (calcd: 3.57%) and the framework decomposition in the temperature range of 340–700 C.