Three Organic–Inorganic Hybrids Based on [MoxOy]n– Chains Decorated with Organic Ligands and Transition‐Metal Coordination Complexes

Abstract

Three new organic–inorganic hybrid compounds, namely, [Cu(Hbib)2(γ‐Mo8O26)] (1), [{Ni(H2O)}2(bib)2(γ‐Mo8O26)]·2H2O (2), and [(atrz)2Mo2O6] (3), [bib = 1‐(1‐imidazolyl)‐4‐(1‐imidazolylmethyl)benzene, atrz = 4‐amino‐4H‐1,2,4‐triazole], have been successfully synthesized under hydrothermal conditions. Crystal structure analysis shows that all of the three compounds contain rare one‐dimensional (1D) infinite oxomolybdenum chains decorated with organic ligands or transition‐metal coordination complexes. Compounds 1 and 2 represent two‐ and three‐dimensional frameworks constructed from the [γ‐Mo8O26]n4n– chain integrated by different transition‐metal coordination complexes, showing a 2D (4)‐connected framework with (44·62) topology and a unique 3D (4,4)‐connected framework with (4·68·8)2(42·62·82) topology, respectively. However, the [γ‐Mo8O26]n4n– anion chains in compounds 1 and 2 are different. The adjacent (γ‐Mo8O26)4– units in 1 are interlinked by µ2‐oxygen atoms, and the (γ‐Mo8O26)4– anion units in compound 2 are interconnected by µ3‐oxygen atoms. Compound 3 consists of 1D chains of {Mo2O4}n decorated by bis(monodentate) atrz ligands through Mo–N bonds. These compounds present good thermostability under 260 °C. The band gaps (Eg) of compounds 1–3 were estimated, suggesting that these inorganic–organic hybrids could be promising semiconductor materials. Compound 1 shows a high capacity to adsorb methylene blue (MB) at room temperature, owing to its special structure and chemical composition, and it can selectively capture MB molecules from binary‐mixture solutions of methyl orange (MO) and MB, or MB and rhodamine B (RhB).