title: An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer.
abstract: The heterometallic complexes trans-[Cp(dppe)FeNCRu(o-bpy)CNFe(dppe)Cp][PF6]n(1[PF6]n, n=2, 3, 4; o-bpy=1,2-bis(2,2'-bipyridyl-6-yl)ethane, dppe=1,2-bis(diphenylphosphino)ethane, Cp=1,3-cyclopentadiene) in three distinct states have been synthesized and fully characterized. 13+[PF6]3and 14+[PF6]4are the one- and two-electron oxidation products of 12+[PF6]2, respectively. The investigated results suggest that 1[PF6]3is a Class II mixed valence compound. 1[PF6]4after a thermal treatment at 400 K shows an unusually delocalized mixed valence state of [FeIII-NC-RuIII-CN-FeII], which is induced by electron transfer from the central RuIIto the terminal FeIIIin 1[PF6]4, which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
authors.forename: Xiao
authors.initials: X
authors.lastname: Ma
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
authors.forename: Chen-Sheng
authors.initials: CS
authors.lastname: Lin
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
authors.forename: Xiao-Quan
authors.initials: XQ
authors.lastname: Zhu
authors.forename: Sheng-Min
authors.initials: SM
authors.lastname: Hu
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
authors.forename: Tian-Lu
authors.initials: TL
authors.lastname: Sheng
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
authors.forename: Xin-Tao
authors.initials: XT
authors.lastname: Wu
keywords: Mössbauer spectroscopy; cyanido bridges; electron transfer; magnetic properties; mixed-valence compounds