Multisite effects on intervalence charge transfer in a clusterlike trinuclear assembly containing ruthenium and osmium

D'Alessandro, Deanna M., Davies, Murray S., and Keene, F. Richard (2006) Multisite effects on intervalence charge transfer in a clusterlike trinuclear assembly containing ruthenium and osmium. Inorganic Chemistry, 45 (4). pp. 1656-1666.

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Abstract

The intervalence charge transfer (IVCT) properties of the mixed-valence forms of the diastereoisomers of the dinuclear [{Ru(bpy)2}(μ-HAT){M(bpy)2}]5+ (M = Ru or Os) complexes and the trinuclear heterochiral [{Ru(bpy)2}2{Os(bpy)2}(μ-HAT)]n+ (n = 7, 8; HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2‘-bipyridine) species display a marked dependence on the nuclearity and extent of oxidation of the assemblies, while small differences are also observed for the diastereoisomers of the same complex in the dinuclear cases. The mixed-valence heterochiral [{Ru(bpy)2}2{Os(bpy)2}(μ-HAT)]n+ (n = 7, 8) forms exhibit IVCT properties that are intermediate between those of the diastereoisomeric forms of the localized hetero-dinuclear complex [{Ru(bpy)2}(μ-HAT){Os(bpy)2}]5+ and the borderline localized-to-delocalized homo-trinuclear complex [{Ru(bpy)2}3(μ-HAT)]n+ (n = 7, 8). The near-infrared (NIR) spectrum of the +7 mixed-valence species exhibits both interconfigurational (IC) and IVCT transitions which are quantitatively similar to those in [{Ru(bpy)2}(μ-HAT){Os(bpy)2}]5+ and are indicative of the localized mixed-valence formulation [{RuII(bpy)2}2{OsIII(bpy)2}(μ-HAT)]7+. The +8 state exhibits a new band attributable to an IVCT transition in the near-infrared region.

Item ID: 4587
Item Type: Article (Refereed Research - C1)
Keywords: trinuclear; intervalence charge transfer; ruthenium; osmium; mixed-valence
ISSN: 1520-510X
Date Deposited: 15 Jun 2009 01:58
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
Citation Count from Web of Science Web of Science 12
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