Influence of Ligand with Fine Difference at Donor Site on MMCT Property in Binuclear Mixed Valence Complexes

• 来源期刊: 结构化学
• 年，卷（期）: 2021,（2）
• 所属期刊栏目: coordination cbemistry
• 页码范围: 207-216
• 页数: 10页
• 语种: 英文
• DOI: 10.14102/j.cnki.0254-5861.2011-2811

摘要

To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in similar mixed-valence(MV)complexes,a series of binuclear organometallic complexes,MeCp(dppe)RuCNFeCl3(1),MeCp(PPh3)2RuCNFeCl3(2),Cp*(dppe)FeCNFeCl3(3),Cp*(dppe)RuCNFeCl3(4)and Cp*(PPh3)2RuCNFeCl3(5),have been synthesized and characterized.The electronic absorptions of these complexes show the presence of MMCT properties between RuⅡ or FeⅡ and FeⅢ ions,strongly supported by the theoretical calculations.With increasing electron-donating ability of ligands(PPh3 ＞ dppe,Cp* ＞MeCp)at donor site,the MMCT absorption bands are red-shifted,which expresses in the sequence of absorption bands with 1(500 nm),4(536 nm),2(542 nm),5(580 nm)from high-energy to low-energy.Meanwhile,the MMCT absorption energy of 4(536 nm)is larger than that of 3(760 nm)due to the stronger electron-donating ability of FeⅡthan Ru1.Furthermore,these complexes belong to the Class Ⅱ systems according to the Robin and Day's classification.