An Effective Strategy To Construct Novel Polyoxometalate-Based Hybrids by Deliberately Controlling Organic Ligand Transformation In Situ

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• 作者：Xiu-Li Wang ; Rui Zhang ; Xiang Wang ; Hong-Yan Lin ; Guo-Cheng Liu
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 5, 2016
• 年：2016
• 卷：55
• 期：13
• 页码：6384-6393
• 全文大小：844K
• 年卷期：0
• ISSN：1520-510X

文摘

Deliberately controlling organic ligand transformation in situ has remained a challenge for the construction of polyoxometalate (POM)-based inorganic–organic hybrids. In this work, four POM-based hybrids assembled from an in situ bifurcating organic ligand—[Cu₂(DIBA)₄](H₃PMo₁₂O₄₀)·6H₂O (1), [Cu₂(DIBA)₄](H₄SiW₁₂O₄₀)·6H₂O (2), [Ag(HDIBA)₂](H₂PMo₁₂O₄₀)·2H₂O (3), [Ag₃(HDIBA)₂(H₂O)][(P₂W₁₈O₆₂)_1/2]·4H₂O (4) (DIBAH = 3,5-di(1H-imidazol-1-yl) benzoic acid)—have been designed and obtained under hydrothermal conditions. Compounds 1 and 2 are isostructural, displaying a three-dimensional (3D) 2-fold interpenetrating framework with two types of channels, and the bigger channels are occupied by Keggin polyoxoanions and crystallization water molecules, but only crystallization water molecules in the smaller ones. Compound 3 displays a 3D supramolecular structure constructed from {Ag(HDIBA)₂} segments and PMo₁₂O₄₀^3– polyoxoanions through hydrogen bonding interactions. Compound 4 shows a 3D 2-fold interpenetrating framework based on (3, 3, 4)-connected network, which is constructed from {Ag₃(HDIBA)₂}_n chains and P₂W₁₈O₆₂^6– polyoxoanions as linkers. The DIBAH ligand was generated in situ from 3,5-di(1H-imidazol-1-yl)benzonitrile by deliberate design, which illustrates that the strategy to construct novel POM-based hybrids by controlling ligand transformation in situ is rational and feasible. In addition, the effects of the central metal and POMs on the structures of the target compounds were discussed. Finally, the electrochemical and photocatalytic properties of compounds 1–4 have been investigated in this paper.