Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis,Quantum Chemical Calculations and Electrochemistry |
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| Authors: | Veronika I. Komlyagina Nikolay F. Romashev Vasily V. Kokovkin Artem L. Gushchin Enrico Benassi Maxim N. Sokolov Pavel A. Abramov |
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| Affiliation: | 1.Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences (SB RAS), 3 Akad. Lavrentiev Ave., 630090 Novosibirsk, Russia;2.Faculty of Natural Sciences, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia;3.Institute of Natural Sciences and Mathematics, Ural Federal University, 620002 Ekaterinburg, Russia |
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| Abstract: | Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[β-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV–Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2. |
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| Keywords: | polyoxomolybdates Ag dpp-bian redox-active ligands complexes crystal structure DFT calculations cyclic voltammetry |
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