Intervalence charge transfer (IVCT) in ruthenium dinuclear and trinuclear assemblies containing the bridging ligand HAT {1,4,5,8,9,12-hexaazatriphenylene}

被引:37
作者
D'Alessandro, DM [1 ]
Keene, FR [1 ]
机构
[1] James Cook Univ N Queensland, Sch Pharm & Mol Sci, Townsville, Qld 4811, Australia
关键词
charge transfer; electrochemistry; mixed-valent compounds; stereochemistry; trinuclear compounds;
D O I
10.1002/chem.200401038
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The lVCT characteristics of the mixed-valence forms of the dinuclear [{Ru(bpy)(2)}(2)(mu-hat)](n+) and the trinuclear [{Ru(bpy)(2)}(3)(mu-hat)](n+) species {HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy=2,2'-bipyridine} show a marked dependence on the nuclearity, and in the trinuclear case on the extent of oxidation. Small differences are also found between the diastereoisomers of the dinuclear complex {meso (AA) and rac (Delta Delta/Lambda Lambda)}, and between the homochiral (Delta(3)/Delta(3)) and heterochiral (Delta(2)Lambda/Lambda(2)Delta) diastereoisomers of the trinuclear case. The strong metal-metal interactions result in unusual spectroscopic and electrochemical properties of the singly-oxidised (+7) and doubly-oxidised (+8) trinuclear mixed-valence species. A qualitative localised bonding description based on the geometrical properties of the d pi(Ru-II/III) orbitals is invoked to explain the IVCT behaviour in the di- and trinuclear systems.
引用
收藏
页码:3679 / 3688
页数:10
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