Journal Articles Inorganic Chemistry Year : 2021

Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [Re(5)MoSe(8)(CN)(6)](n)

Abstract

The heterometallic cluster-based compound K[ReMoSe(CN)] was obtained by high-temperature reaction from a mixture of ReSe and MoSe in molten potassium cyanide. The redox behavior of the [ReMoSe(CN)] cluster anion was studied by cyclic voltammetry in aqueous and organic media showing two reversible one-electron-redox transitions with of -0.462 and 0.357 V versus Ag/AgCl in CHCN. Aqueous media potentials were found to be noticeably shifted to higher values because of solvation. Chemically accessible potentials allowed us to structurally isolate and characterize the [ReMoSe(CN)] ( = 3-, 4-, and 5-) cluster complex in several charge states with corresponding cluster skeletal electron (CSE) numbers ranging from 24 to 22. The electronic absorption of the [ReMoSe(CN)] cluster complex varies significantly upon a change of the CSE number, especially in the visible and near-IR regions. The local cluster core distortion upon electron removal was confirmed by density functional theory calculation, while the overall geometry of the cluster anion remained practically unaltered.

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Dates and versions

hal-03247561 , version 1 (03-06-2021)

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Viktoria K Muravieva, Ivan P Loginov, Taisiya S Sukhikh, Maxim R Ryzhikov, Vadim V Yanshole, et al.. Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [Re(5)MoSe(8)(CN)(6)](n). Inorganic Chemistry, 2021, 60 (12), pp.8838-8850. ⟨10.1021/acs.inorgchem.1c00763⟩. ⟨hal-03247561⟩
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