Syntheses and Characterizations of Cyanido-bridged Dinuclear Ru-complexes and Their MMCT Properties in the One-electron Oxidation State  

作　　者：LIU Yang ZHU Xiao-Quan WU Xin-Tao SHENG Tian-Lu 

机构地区：[1]College of Chemistry,Fuzhou University,Fuzhou 350002,China [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Journal of Structural Chemistry》2021年第10期1253-1264,共12页结构化学（英文）

基　　金：the National Science Foundation of China(21773243,21973095);the Strategic Priority Research Program of Chinese Academy of Sciences(XDB20010200)for financial support。

摘　　要：We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the precursor.All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis.The one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible range.The MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.

关 键 词：electron transfer MIXED-VALENCE metal to metal charge transfer(MMCT) cyanide bridge 

分 类 号：O641.4[理学—物理化学]