Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene |
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| Authors: | Si‐Hai Wu Jiang‐Yang Shao Hong‐Wei Kang Prof. Dr. Jiannian Yao Prof. Dr. Yu‐Wu Zhong |
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| Affiliation: | 1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China) http://zhongyuwu.iccas.ac.cn/;2. University of Chinese Academy of Sciences, Beijing 100049 (P.R. China);3. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093 (P.R. China) |
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| Abstract: | Four heterodimetallic complexes [Ru(Fcdpb)(L)](PF6) (Fcdpb=2‐deprotonated form of 1,3‐di(2‐pyridyl)‐5‐ferrocenylbenzene; L=2,6‐bis‐(N‐methylbenzimidazolyl)‐pyridine (Mebip), 2,2′:6′,2′′‐terpyridine (tpy), 4‐nitro‐2,2′:6′,2′′‐terpyridine (NO2tpy), and trimethyl‐4,4′,4′′‐tricarboxylate‐2,2′:6′,2′′‐terpyridine (Me3tctpy)) have been prepared. The electrochemical and spectroelectrochemical properties of these complexes have been examined in CH2Cl2, CH3NO2, CH3CN, and acetone. These complexes display two consecutive redox couples owing to the stepwise oxidation of the ferrocene (Fc) and ruthenium units, respectively. The potential difference, ΔE1/2 (E1/2(RuII/III)?E1/2(Fc0/+)), decreased slightly with increasing solvent donocity. The mixed‐valent states of these complexes have been generated by electrolysis and the resulting intervalence charge‐transfer (IVCT) bands have been analyzed by Hush theory. Good linear relationships exist between the energy of the IVCT band, Eop, and ΔE1/2 of four mixed‐valent complexes in a given solvent. |
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| Keywords: | ferrocene metalation mixed‐valent compounds redox chemistry ruthenium |
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