title: Conformational Tuning of the Intramolecular Electronic Coupling in Molecular-Wire Biruthenium Complexes Bridged by Biphenyl Derivatives.
abstract: The synthesis and characterization of a series of biphenyl-derived binuclear ruthenium complexes with terminal {RuCl(CO)(PMe3)3} moieties and different structural arrangements of the phenyl rings are reported. Electrochemical studies revealed that the two metal centers of the binuclear ruthenium complexes interact with each other through the biphenyl bridge, and the redox splittings ΔE1/2 show a strong linear correlation with cos(2)  ϕ, where ϕ is the torsion angle between the two phenyl rings. A combination of electrochemical, UV/Vis/NIR, and in situ IR differential spectroelectrochemical analysis clearly showed that: 1) the intramolecular electronic couplings in the binuclear ruthenium complexes could be modulated by changing ϕ; 2) the electronic ground state of the mixed-valent cations changes from delocalized to localized through the biphenyl bridge with increasing torsion angle ϕ, that is, the redox processes of these complexes change from significant involvement of the bridging ligand to an oxidation behavior with less participation of the bridge.
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Dan-Dan
authors.initials: DD
authors.lastname: Kong
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Lu-Sha
authors.initials: LS
authors.lastname: Xue
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Rui
authors.initials: R
authors.lastname: Jang
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Bin
authors.initials: B
authors.lastname: Liu
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Xiang-Gao
authors.initials: XG
authors.lastname: Meng
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China). jinshan@mail.ccnu.edu.cn.
authors.forename: Shan
authors.initials: S
authors.lastname: Jin
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Ya-Ping
authors.initials: YP
authors.lastname: Ou
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China).
authors.forename: Xiao
authors.initials: X
authors.lastname: Hao
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079 (P. R. China). chshliu@mail.ccnu.edu.cn.
authors.forename: Sheng-Hua
authors.initials: SH
authors.lastname: Liu
keywords: bridging ligands; electrochemistry; mixed-valent compounds; redox chemistry; ruthenium