Influence of Transition Metal Coordination Nature on the Assembly of Multinuclear Subunits in Polyoxometalates-Based Compounds

Abstract

Four inorganic−organic hybrids based on Keggin-type polyoxometalate (POM), [Ag3(bmte)2(PMo12O40)] (1), [CuI3(bmte)3(PMo12O40)] (2), [CuII(bmte)3(HPMo12O40)] (3), and [Ni(bmte)3(HPMo12O40)] (4) (bmte = 1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane), have been synthesized under hydrothermal conditions by tuning the coordination nature of transition metal (TM) ions. The transformation of coordination modes of TM ions has a crucial influence on the multinuclear structures of this series. In compound 1, binuclear subunits [Ag(1)2(bmte)2]2+ occur, which is connected by PMo12O403− (PMo12) anions to construct a one-dimensional (1D) chain. Furthermore, these chains are linked by Ag(2) ions acting as fuses to construct a two-dimensional (2D) gridlike sheet. Compound 2 shows trinuclear clusters, [CuI3(bmte)3]3+, which are also connected by PMo12 anions to construct a 1D chain. These two neighboring chains arrange like a “zipper”. Compounds 3 and 4 are isostructural. In compound 3, the metal−organic subunit is...