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

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2005年 / 11卷 / 12期

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

页码：3679 / 3688

页数：10

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