Influence of Substitution Effect on MMCT in Mixed‐Valence Cyanido‐Bridged FeII−CN−Ru2III,III−NC−FeII System

Abstract

AbstractThis work reports the designed synthesis and characterization of nine tetranuclear mixed valence cyanido‐bridged complexes [CpMen(dppe)FeIICNRu2III,III(X‐DMBA)4NCFeII(dppe)CpMen][PF6]2 (1–9: CpMen=polymethylcyclopentadienyl, n=0, 4, 5; DMBA=N,N’‐dimethylbenzamidinate, X= H, MeO, CF3). The regular variation of crystallographic data, IR and UV/Vis/NIR spectra for complexes 1–9 demonstrates that the substitution effect of the ligand at the donor or acceptor fragment has explicit influence on the MMCT properties. Moreover, the electrochemical measurement might suggest the existence of long‐range electronic coupling between the two terminal FeII in this FeII−CN−Ru2III,III−NC−FeII array.