title: Asymmetric mixed-valence complexes that consist of cyclometalated ruthenium and ferrocene: synthesis, characterization, and electronic-coupling studies.
abstract: Three bis-tridentate ferrocene-containing cyclometalated ruthenium complexes, [(Fcdpb)Ru(tpy)](+) (1(+)), [(Fctpy)Ru(dpb)](+) (2(+)), and [(Fcdpb)Ru(Fctpy)](+) (3(+)), have been prepared and characterized, where Fcdpb is the 2-deprotonated form of 1,3-di(2-pyridyl)-5-ferrocenylbenzene, tpy is 2,2':6',2"-terpyridine, dpb is the 2-deprotonated form of 1,3-di(2-pyridyl)benzene, and Fctpy is 4'-ferrocenyl-2,2':6',2"-terpyridine. Single crystals of compounds 2(+) and 3(+) have been studied by X-ray analysis. Complexes 1(+) and 2(+) displayed two anodic redox waves, whilst three well-separated redox couples were observed for compound 3(+). A combined experimental and computational study suggested that the ferrocene unit on the Fcdpb moiety in compounds 1(+) and 3(+) was oxidized first. In contrast, the order of the oxidation of ruthenium and ferrocene in complex 2(+) was reversed. Metal-to-metal-charge-transfer transitions (MM'CT) have been observed for the singly oxidized states 1(2+), 2(2+), and 3(2+) in the near-infrared region. Hush analysis showed that the metal-metal electronic couplings in compounds 1(2+) and 3(2+) were much stronger than those in compound 2(2+).
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Bejing 100190, People's Republic of China.
authors.forename: Si-Hai
authors.initials: SH
authors.lastname: Wu
authors.forename: Jun-Jian
authors.initials: JJ
authors.lastname: Shen
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao
authors.forename: Yu-Wu
authors.initials: YW
authors.lastname: Zhong