An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer

作者：Ma, Xiao; Lin, Chen-Sheng; Zhu, Xiao-Quan; Hu, Sheng-Min; Sheng, Tian-Lu^*; Wu, Xin-Tao

来源：Angewandte Chemie - International Edition, 2017, 56(6): 1605-1609.

DOI：10.1002/anie.201610855

• cyanido bridges
• electron transfer
• magnetic properties
• mixed-valence compounds
• Mossbauer spectroscopy

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. 1(3+)[PF6](3) and 1(4+)[PF6](4) are the one- and two-electron oxidation products of 1(2+)[PF6](2), respectively. The investigated results suggest that 1[PF6](3) is a ClassII mixed valence compound. 1[PF6](4) after a thermal treatment at 400K shows an unusually delocalized mixed valence state of [Fe-III-NC-Ru-III-CN-Fe-II], which is induced by electron transfer from the central Ru-II to the terminal Fe-III in 1[PF6](4), which was confirmed by IR spectroscopy, magnetic data, and EPR and Mossbauer spectroscopy.

• 出版日期2017-2-1
• 单位结构化学国家重点实验室; 中国科学院福建物质结构研究所