title: Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state.
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.
authors.affiliation: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. ohtani@sci.kumamoto-u.ac.jp hayami@sci.kumamoto-u.ac.jp.
authors.forename: Ryo
authors.identifier: http://orcid.org/0000-0003-4840-3338
authors.initials: R
authors.lastname: Ohtani
authors.affiliation: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. ohtani@sci.kumamoto-u.ac.jp hayami@sci.kumamoto-u.ac.jp.
authors.forename: Yuu
authors.initials: Y
authors.lastname: Kitamura
authors.affiliation: Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan.
authors.forename: Yuh
authors.initials: Y
authors.lastname: Hijikata
authors.affiliation: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. ohtani@sci.kumamoto-u.ac.jp hayami@sci.kumamoto-u.ac.jp.
authors.forename: Masaaki
authors.initials: M
authors.lastname: Nakamura
authors.affiliation: School of Chemistry, The University of Sydney, NSW 2006, Australia.
authors.forename: Leonard F
authors.initials: LF
authors.lastname: Lindoy
authors.affiliation: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. ohtani@sci.kumamoto-u.ac.jp hayami@sci.kumamoto-u.ac.jp and Institute of Pulsed Power Science (IPPS), Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors.forename: Shinya
authors.identifier: http://orcid.org/0000-0001-8392-2382
authors.initials: S
authors.lastname: Hayami