Wang Xiu-Li, Zhang Rui, Wang Xiang, Lin Hong-Yan, Liu Guo-Cheng
Department of Chemistry, Bohai University , Jinzhou, 121000, People's Republic of China.
Inorg Chem. 2016 Jul 5;55(13):6384-93. doi: 10.1021/acs.inorgchem.6b00009. Epub 2016 Jun 20.
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)4·6H2O (1), Cu2(DIBA)4·6H2O (2), Ag(HDIBA)2·2H2O (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.
对于基于多金属氧酸盐（POM）的无机-有机杂化物的构建而言，原位可控地调控有机配体的转化仍然是一项具有挑战性的工作。在本研究中，通过水热法设计并合成了四种基于POM的杂化物，它们由原位分叉的有机配体组装而成，分别为Cu2(DIBA)4·6H2O (1)、Cu2(DIBA)4·6H2O (2)、Ag(HDIBA)2·2H2O (3)、[Ag3(HDIBA)2(H2O)][(P2W18O62)1/2]·4H2O (4)（DIBAH = 3,5-二(1H-咪唑-1-基)苯甲酸）。化合物1和2是同构的，呈现出具有两种类型通道的三维（3D）2重互穿框架，较大的通道被Keggin多金属氧酸根阴离子和结晶水分子占据，而较小的通道中仅存在结晶水分子。化合物3展示出由{Ag(HDIBA)2}片段和PMo12O40(3-)多金属氧酸根阴离子通过氢键相互作用构建而成的3D超分子结构。化合物4呈现出基于(3, 3, 4)-连接网络的3D 2重互穿框架，它由{Ag3(HDIBA)2}n链和P2W18O62(6-)多金属氧酸根阴离子作为连接体构建而成。通过精心设计，DIBAH配体由3,5-二(1H-咪唑-1-基)苯甲腈原位生成，这表明通过原位控制配体转化来构建新型基于POM的杂化物的策略是合理且可行的。此外，还讨论了中心金属和POM对目标化合物结构的影响。最后，本文研究了化合物1 - 4的电化学和光催化性能。
