Three Hybrid Organic−Inorganic Assemblies Based on Different Arsenatomolybdates and Cu^II−Organic Units

Three new extended arsenatomolybdates constructed from different As−Mo−O cluster units and Cu-based complex bridges, namely, (As6CuMo6O30){[Cu(imi)4]3[As6CuMo6O30]}2·6H2O (1), [Cu(enMe)2]3[As3Mo3O15]2·2H2O (2), and (NH4)10{Cu(H2O)4}[AsMo6O21(OAc)3]2·12H2O (3) (imi = imidazole, enMe = 1,2-propane diamine, OAc = acetate), were obtained by modulating the organic ligands in the conventional solution and similar conditions. Their structures were determined by single-crystal X-ray diffraction analysis and were further characterized by elemental analysis, IR, fluorescent spectroscopy, and TG analysis. The structure of 1 is constructed from [As6CuMo6O30]4− anionic clusters and [Cu(imi)4]2+ complex subunits via Cu−O interactions to form a two-dimensional (2D) framework with 436 topology structure. Compound 2 is constructed from [As3Mo3O15]3− anionic clusters and [Cu(enMe)2]2+ complex subunits via Cu−O interactions to form a 2D honeycomb framework with 63 topology structure. Compound 3 is based on the unprecedented functionalized polyanions [AsMo6O21(OAc)3]6−; two of them are bridged by a {Cu(H2O)42+ complex to form a dimeric polyanion {Cu(H2O)4[AsMo6O21(OAc)3]2}10−, and the dimeric polyanions are further connected via hydrogen bonds to three-dimensional supramolecular structure. Compound 1 has an intense emission at 399 nm assigned to O2p to Mo4d charge transfer and may be an excellent candidate for potential solid-state photofunctional material.