Synthesis and Crystal Structure of the Azide K4[Re6Sei8(N3)a6]·4H2O; Luminescence,Redox, and DFT Investigations of the [Re6Sei8(N3)a6]4– Cluster Unit |
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| Authors: | Aurore Gandubert Konstantin A Brylev Thi Thuong Nguyen Nikolai G Naumov Noboru Kitamura Yann Molard Régis Gautier Stéphane Cordier |
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| Institution: | 1. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS – Université de Rennes 1 – ENSC Rennes, Campus de Beaulieu, Avenue du général Leclerc, 35042 Rennes Cedex (France);2. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev pr.630090 Novosibirsk, Russia;3. Department of Chemistry, Faculty of Science, Hokkaido University, 060–0810 Sapporo, Japan |
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| Abstract: | The reaction of K4Re6Sei8(OH)a6] · 8H2O with NaN3 in water results in the formation of Re6Sei8(N3)a]4– units that crystallize with K+ and H2O to form K4Re6Sei8(N3)a6] · 4H2O P21/c (N°14), a = 9.0595(3) Å, b = 13.2457(4) Å, c = 13.2040(5) Å, β = 94.472(1)°]. In the solid state, the unit is characterized by N3 linear groups forming bond angles of roughly 120° with the Re6 cluster. The positions of the νas and νsy bands as well as N–N–N deformation modes of the N3 groups are discussed. Luminescence properties of the Re6Sei8(N3)a]4– unit were measured in the solid state and in an acetonitrile solution. The redox potential of the Re6Sei8(N3)a]4–/Re6Sei8(N3)a]3– system was measured in acetonitrile. Experimental results were analyzed in the light of density functional theory calculations. |
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| Keywords: | Cluster compounds Luminescence Azides Density functional calculations Crystal structure |
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