Abstract
Two reduced Keggin-type hybrid assemblies modified by Cu-biz and/or Cu-bdz complexes, (Cu(biz)2)4[{Cu(biz)2}2{(VO)2(PMoVI5MoV7O40)}]·2H2O (1) and {Cu(biz)2}4[{Cu(bdz)}{PMoVI10MoV2O40}]·H2O (2) (biz = benzimidazole; bdz = benz- 1,3,4,6-dimidazolium) were obtained by hydrothermal reaction and structurally characterized by routine instrumental techniques. Compound 1 is a deep reduced polyoxoanion {PMo5VIMo7VO40} capped by two {VO4} tetrahedrons on two trenches surrounded by opposite {Mo4O18} aggregation units, which represents the first hepta-electron reduced bivanadiuml cap assembly. The bicapped unit bonds to two symmetrical {Cu(biz)2} fragments to form a bisupported and bicapped cluster, which is further extended to a 3D supramolecular network with holes via weak interactions. Compound 2 is a covalent 1D chain consisted of bielectron reduced Keggin cluster and unique binuclear complex {Cu2(bdz)2} linker, in which in situ ligands of bdz from bzi and imi precursor was observed for the first time. Compounds 1 and 2 exhibit dual functional electrocatalytic activities for reduction of iodates (IO3−) and oxidation of dopamine (DA) as well as high efficiency photocatalytic behaviors for the decomposition of typical azo dyes under UV irradiation.
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