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Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores
Authors:Aleksei S Pronin  Spartak S Yarovoy  Yakov M Gayfulin  Aleksey A Ryadun  Konstantin A Brylev  Denis G Samsonenko  Ilia V Eltsov  Yuri V Mironov
Institution:1.Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Acad. Lavrentiev ave., 630090 Novosibirsk, Russia; (A.S.P.); (S.S.Y.); (A.A.R.); (K.A.B.); (D.G.S.);2.Department of Natural Sciences, Novosibirsk State University, 2, Pirogova str., 630090 Novosibirsk, Russia;
Abstract:Compounds based on new cyanide cluster anions {Mo6I8}(CN)6]2–, trans-{Mo6I8}(CN)4(MeO)2]2– and trans-{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands.
Keywords:cluster compounds  molybdenum  tungsten  cyanide ligand  crystal structure  luminescence  hydrolytic stability
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