Urea-bridged diferrocene: structural, electrochemical, and spectroelectrochemical studies  

作　　者：Zhong-Liang Gong Yu-Wu Zhong 

机构地区：[1]Beijing National Laboratory for Molecular Sciences [2]CAS Key Laboratory of Photochemistry [3]Institute of Chemistry, Chinese Academy of Sciences

出　　处：《Science China Chemistry》2015年第9期1444-1450,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21271176,91227104,21472196,21221002);the National Basic Research Program of China(2011CB932301);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB 12010400)

摘　　要：Urea-bridged diferrocene derivatives N,N?-diferrocenylurea(1) and N,N?-dimethyl-N,N?-diferrocenylurea(2) were prepared and characterized. Single-crystal X-ray analysis shows that Compound 1 has a trans-trans linear conformation whereas Compound 2 has a trans-cis conformation. Both compounds display two consecutive redox couples with, respectively, E1/2 of +0.29 and +0.42 V vs. Ag/Ag Cl for 1 and +0.31 and +0.50 V for 2. Spectroelectrochemical studies show the presence of distinct intervalence charge transfer(IVCT) transitions for the one-electron-oxidized mixed-valent Compound 1+, with an estimated electronic coupling parameter of 190 cm?1. By contrast, the one-electron-oxidized Compound 2+ shows much weaker IVCT transitions.Urea-bridged diferrocene derivatives N,N＂-diferrocenylurea（1） and N,N＂-dimethyl-N,N＂-diferrocenylurea（2） were prepared and characterized. Single-crystal X-ray analysis shows that Compound 1 has a trans-trans linear conformation whereas Compound 2 has a trans-cis conformation. Both compounds display two consecutive redox couples with, respectively, E1/2 of ＋0.29 and ＋0.42 V vs. Ag/Ag Cl for 1 and ＋0.31 and ＋0.50 V for 2. Spectroelectrochemical studies show the presence of distinct intervalence charge transfer（IVCT） transitions for the one-electron-oxidized mixed-valent Compound 1＋, with an estimated electronic coupling parameter of 190 cm^-1. By contrast, the one-electron-oxidized Compound 2＋ shows much weaker IVCT transitions.

关 键 词：mixed-valent compounds FERROCENE ELECTROCHEMISTRY UREA SPECTROELECTROCHEMISTRY 

分 类 号：O627.81[理学—有机化学]