By changing the polyoxoanions in the same metal–organic system (Ag/ptz), two novel inorganic–organic hybrids: [Ag10(ptz)5(HP2W18O62)(H2O)4]·2H2O (1), [Ag7(ptz)5(H2SiW12O40)(H2O)] (2) (ptz = 5-(4-pyridyl)-tetrazolate), are synthesized under hydrothermal conditions, and characterized by IR spectra, elemental analyses and single crystal X-ray diffraction. Compound 1 and 2 show 3D POM-templated framework structures. In compound 1, a 2D layer is constructed by “shield-like” metal–organic circles templated by P2W18 polyoxoanions, which is extended to a 3D structure by covalent bonds in an interdigital mode. In compound 2, a 3D network is constructed by 2D layers and a “double bridge-pillar”, the Keggin polyoxoanion templates are enveloped in pairs in nanocages. The influences of polyoxoanion templates on the frameworks are discussed. The electrochemical behavior and luminescent properties for compound 1 and 2 are investigated.
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