Driving the localized-to-delocalized transition in unsymmetrical dinuclear ruthenium mixed-valence complexes

D'Alessandro, Deanna M., and Keene, F. Richard (2005) Driving the localized-to-delocalized transition in unsymmetrical dinuclear ruthenium mixed-valence complexes. Australian Journal of Chemistry, 58 (11). pp. 767-777.

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Abstract

The degree of delocalization in the symmetrical complexes [{Ru(bpy)2}2(μ-dpb′)]5+ and [{Ru(bpy)2}2(μ-dpb)]5+ (dpb = 2,3-bis(2-pyridyl)-1,4-benzoquinoxaline; dpb′ = dipyrido(2,3-a;3′,2′-c)benzophenazine; bpy = 2,2′-bipyridine) is diminished by the substitution of the terminal bpy ligands at one end of the complex. The results of a classical analysis for the diastereoisomeric forms of the series of complexes [{Ru(bpy)2}(μ-BL){Ru(pp)2}]5+ (pp = bpy, Me2bpy (4,4′-dimethyl-2,2′-bipyridine), Me4bpy (4,4′,5,5′-tetramethyl-2,2′-bipyridine)) indicate that a greater degree of ground-state delocalization exists in the complexes incorporating the bridging ligand dpb′ compared with the dpb analogue. A two-state analysis in which ΔE 0 (the redox asymmetry) is varied at constant H ab (the electronic coupling) and λ (the reorganizational energy) does not adequately describe the properties of the systems due to the importance of a third electronic state corresponding to the bridging ligand.

Item ID: 4548
Item Type: Article (Refereed Research - C1)
Keywords: dinuclear; intervalence charge transfer; localisation; mixed-valence; ruthenium; stereochemistry
ISSN: 1445-0038
Date Deposited: 12 Jun 2009 05:54
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
Citation Count from Web of Science Web of Science 3
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