D'Alessandro, Deanna M., and Keene, F. Richard (2005) Intervalence charge transfer (IVCT) in ruthenium dinuclear and trinuclear assemblies containing the bridging ligand HAT {1,4,5,8,9,12-hexaazatriphenylene}. Chemistry: a European journal, 11 (12). pp. 3679-3688.

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Abstract

The IVCT characteristics of the mixed-valence forms of the dinuclear [{Ru(bpy)2}2(µ-hat)]n+ and the trinuclear [{Ru(bpy)2}3(µ-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 (∆Λ) and rac (∆∆/ΛΛ)}, and between the homochiral (∆3/Λ3) and heterochiral (∆2Λ/Λ2∆) 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 dΠ(RuII/III) orbitals is invoked to explain the IVCT behaviour in the di- and trinuclear systems.

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