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Polyoxometalate-Based Metal−Organic Frameworks Assembled under the Ionothermal Conditions

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posted on 2011-02-02, 00:00 authored by Hai Fu, Yangguang Li, Ying Lu, Weilin Chen, Qiong Wu, Jingxin Meng, Xiaolan Wang, Zhiming Zhang, Enbo Wang
One new polyoxometalate compound H3(Tea)(Bmim)3[P2W18O62]·3H2O (Tea = triethylamine, Bmim = 1-methyl-3-ethylimidazole) (1) and three new polyoxometalate-based metal−organic frameworks (PMOFs) CuII(Bbi)1.5(H2Bbi)2[P2W18O62] (Bbi = 1,1-(1,4-butanediyl)-bis(imidazole)) (2), CuII2.5(Mimin)(HMimin)(Bbi)3[P2W18O62]·3H2O (Mimin = methylimidazol) (3), and CuII(Bbtz)(H2Bbi)(H2Btp)[P2W18O62] (Bbtz = 1,4-bis(triazol-1-ylmethyl)benzene, Btp = 1,3-Bis(1,2,4-triazol-1-yl)propane) (4) have been synthesized under ionothermal conditions using an ionic liquid (IL) [Bmim]Br (Bmim = 1-ethyl-3-methylimidazole) as solvent. Their structures were determined by single crystal X-ray diffraction. Compound 1 possesses a one-dimensional (1D) supramolecular chain-like structure constructed from [P2W18O62]6− anions, Bmim, Tea, and water molecules. Compound 2 has a two-dimensional (2D) (6,3)-layer structure built by [P2W18O62]6− anions, copper ions, and Bbi ligands. Compounds 3 and 4 are three-dimensional (3D) PMOFs with novel (6.8.10)(4.6.83.10)(4.6.83.12) and classic (65.8)(65.8)-cds topologies, respectively. Compounds 24 represent the first examples of PMOFs synthesized by the ionothermal method. The successful synthesis of compounds 24 suggests that ionothermal synthesis will be a very promising synthetic technique for assembling new PMOFs. Additionally, the properties of the four compounds have been studied in detail.

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