title: Transition from a Metal-Localized Mixed-Valence Compound to a Fully Delocalized and Bridge-Biased Electrophore in a Ruthenium-Amine-Ruthenium Tricenter System.
abstract: A series of cyclometalated diruthenium complexes with a redox-active amine bridge were synthesized. Depending on the terminal ligands of the ruthenium components and the substituent on the amine unit, the one-electron-oxidized state can be either in the form of a weakly or strongly coupled mixed-valence diruthenium complex, a fully charge-delocalized three-center system, or a bridge-biased electrophore. This transition among different electronic forms was supported by electrochemistry, near-infrared absorption, electron paramagnetic resonance, and density functional theory analysis.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.|University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
authors.forename: Jian-Hong
authors.initials: JH
authors.lastname: Tang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Jiang-Yang
authors.initials: JY
authors.lastname: Shao
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Yan-Qin
authors.initials: YQ
authors.lastname: He
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Si-Hai
authors.initials: SH
authors.lastname: Wu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.|University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China. zhongyuwu@iccas.ac.cn.|University of Chinese Academy of Sciences, Beijing, 100049, P.R. China. zhongyuwu@iccas.ac.cn.
authors.forename: Yu-Wu
authors.initials: YW
authors.lastname: Zhong
keywords: density functional calculations; electrochemistry; electron transfer; mixed-valence compounds; ruthenium