Construction of Metal-Imidazole-Based Dicarboxylate Networks with Topological Diversity: Thermal Stability, Gas Adsorption, and Fluorescent Emission Properties
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- 作者：Zhi-Gang Gu ; Yi-Ting Liu ; Xu-Jia Hong ; Qing-Guang Zhan ; Zhi-Peng Zheng ; Sheng-Run Zheng ; Wei-Shan Li ; She-Jun Hu ; Yue-Peng Cai
- 刊名：Crystal Growth & Design
- 出版年：2012
- 出版时间：May 2, 2012
- 年：2012
- 卷：12
- 期：5
- 页码：2178-2186
- 全文大小：768K
- 年卷期：v.12,no.5(May 2, 2012)
- ISSN：1528-7505
文摘
Six new metal鈥搊rganic frameworks (MOFs), namely, [Pb(H2IDC)2(H2O)]n (1), {[Pb(H2IEDC)2)]路3H2O}n (2), [Ca2(HIDC)2(H2O)]n (3), {[Ca2(IEDC)2(H2O)2]路H2O}n(4), {[Cd(HIDC)(H2O)]n (5), and {[Cd2(HIEDC)2路3H2O}n (6) (H3IDC = 4,5-imidazoledicarboxylic acid, H3IEDC = 2-ethyl-1H-imidazole-4,5-dicarboxylic acid) were hydrothermally synthesized and characterized. Single-crystal X-ray diffraction shows the ligand H3IDC is partially deprotonated with H2IDC鈥?/sup> and HIDC2鈥?/sup> forms in three corresponding compounds 1, 3, and 5, meanwhile ligand H3IEDC also presents different deportonated motifs of H2IEDC鈥?/sup>, IEDC3鈥?/sup>, and HIEDC2鈥?/sup> in 2, 4, and 6, respectively. Moreover, these partially or fully deportonated ligands coordinate in the 渭1 to 渭5 manner to generate one-dimensional (1D) 鈫?three-dimensional (3D) coordination polymers, displaying 10 different coordination modes. Both 1 and 2 have 3D supramolecular networks assembled via hydrogen bonding interactions but different in structure topologies. Complex 1 is a 1D coordination chain and 2 has a two-dimensional (2D) wave layer-like structure with 44 topology. Complex 3 is a 3D MOF with 310路425路510 topology built up from linear 2-connected HIDC2鈥?/sup> as a linker and 10-connected tetranuclear metal unit [Ca4(渭2-O)6] as a node. However, complex 4 presents a 2D MOF with 36路46路53 topology. Different from 3 and 4, with the 4-connected binuclear metal unit [Cd(O鈥揅鈥揙)]2 as a node, a wave-like 2D MOF with 44 topology in 5 based on H3IDC is created. Complex 6 shows a 3D coordination framework containing 1D alternately arranged hydrophilic channels including (H2O)4 clusters and hydrophobic channels partially occupied by ethyl groups from imidazole rings, in which the Cd(II) ion is viewed as a 4-connected node, and HIEDC2鈥?/sup> and 渭2-O are regarded as two different linkers, 6 showing 42路84 topology. Obviously, these results reveal that the existence of the substitute groups of 2-position in such 4,5-imidazoledicarboxylate ligand plays a critical role in the structural direction of these MOFs. Meanwhile, the adsorption and photoluminescent properties of the selected compounds are investigated.