Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state

Ryo Ohtani, Yuu Kitamura, Yuh Hijikata, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [MnV(N)(CN)4]2−, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH2)n−1-CH3]2[Mn(N)(CN)4(H2O)]·xH2O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [MnV(N)(CN)4]2− anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [MnV(N)(CN)4]2− to [MnVI(N)(CN)4]2− and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)4]2− structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.

Original languageEnglish
Pages (from-to)3749-3754
Number of pages6
JournalDalton Transactions
Volume46
Issue number11
DOIs
Publication statusPublished - Jan 1 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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