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Hydrothermal Synthesis, Structures, and Luminescent Properties of Seven d10 Metal−Organic Frameworks Based on 9,9-Dipropylfluorene-2,7-Dicarboxylic Acid (H2DFDA)

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posted on 04.03.2009, 00:00 by Hua-Dong Guo, Xian-Min Guo, Stuart R. Batten, Jiang-Feng Song, Shu-Yan Song, Song Dang, Guo-Li Zheng, Jin-Kui Tang, Hong-Jie Zhang
A series of Zn(II) and Cd(II) metal−organic frameworks, namely, [Zn(DFDA)] (1), [Cd(DFDA)(C2H5OH)] (2), [Zn2(DFDA)2(L1)2]2·3H2O (3), [Cd2(DFDA)2(L1)2] (4), [Zn(DFDA)(L2)] (5), [Cd(DFDA)(L2)(DMF)] (6), and [Zn(DFDA)(L3)] (7) (where DFDA = 9,9-dipropylfluorene-2,7-dicarboxylate anion, L1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L2 = 1,1′-(1,4-butanediyl) bis(imidazole), L3 = 2,2′-bipyridine) have been synthesized under hydrothermal conditions and structurally characterized. Compound 1 exhibits a three-dimensional (3D) framework containing one-dimensional (1D) Zn(II)-O clusters, with (48·67) topology. Compound 2 contains hydrophobic channels built from infinite 1D Cd(II)-O clusters, with (48·54·63) topology. Compounds 3 and 4 possess isomorphic two-dimensional (2D) layer structures which contain two kinds of rings, and the layers interdigitate extensively. Compound 5 features a 3D diamond-like structure that contains four interpenetrating networks. Compound 6 displays a 2D (4,4) topology. Compound 7 is composed of 1D zigzag chains that are entangled through π−π stacking interactions to generate three interpenetrating diamond-like networks. The potential of ligand H2DFDA to produce interesting metal−organic frameworks is investigated. In particular, the effects of the coordination modes of carboxylates on the formation of different frameworks are evaluated. Thermogravimetric analyses (TGA) for these compounds are discussed. Luminescent studies show that 17 exhibit strong blue fluorescent emissions.