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Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene
Author(s) -
Wu SiHai,
Shao JiangYang,
Kang HongWei,
Yao Jiannian,
Zhong YuWu
Publication year - 2013
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201300739
Subject(s) - chemistry , terpyridine , ruthenium , ferrocene , electrochemistry , solvent , bulk electrolysis , redox , deprotonation , pyridine , substituent , medicinal chemistry , photochemistry , electron transfer , acetone , inorganic chemistry , cyclic voltammetry , organic chemistry , metal , catalysis , electrode , ion
Four heterodimetallic complexes [Ru(Fcdpb)(L)](PF 6 ) (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 (NO 2 tpy), and trimethyl‐4,4′,4′′‐tricarboxylate‐2,2′:6′,2′′‐terpyridine (Me 3 tctpy)) have been prepared. The electrochemical and spectroelectrochemical properties of these complexes have been examined in CH 2 Cl 2 , CH 3 NO 2 , CH 3 CN, 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, Δ E 1/2 ( E 1/2 (Ru II/III )− E 1/2 (Fc 0/+ )), 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, E op , and Δ E 1/2 of four mixed‐valent complexes in a given solvent.