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Four SiMo12O404– (SiMo12)-based compounds, namely, [Ag6Cl2(mmt)4(H4SiMo12O40)(H2O)2] (1), [Ag4(bmte)2(H2O)2(SiMo12O40)] (2), [Ag4(bmtr)2(H2O)2(SiMo12O40)] (3), and [Ag4(bmtb)3(SiMo12O40)] (4) (mmt = 1-methyl-5-mercapto-1,2,3,4-tetrazole, bmte = 1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane, bmtr = 1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane, bmtb = 1,4-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)butane), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction analyses reveal that insertion of -(CH2)n- spacers into the reactant mmt ligand plays important roles in constructing multinuclear AgI clusters in the title compounds and tuning the formation of different multinuclear AgI clusters. In compound 1, the mmt ligands link AgI ions forming a three-dimensional non-multinuclear self-penetrating framework with large dimension channels occupied by SiMo12 polyanions. In 2, a tetranuclear [Ag4(bmte)2(H2O)2]4+ and SiMo12 anions arrange alternately forming a one-dimensi...

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...