【摘 要】
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To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in simila
【机 构】
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State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter
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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.
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