Premium
Intervalence Charge Transfer (IVCT) in Ruthenium Dinuclear and Trinuclear Assemblies Containing the Bridging Ligand HAT {1,4,5,8,9,12‐hexaazatriphenylene}
Author(s) -
D'Alessandro Deanna M.,
Keene F. Richard
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401038
Subject(s) - bridging (networking) , ruthenium , chemistry , bridging ligand , crystallography , charge (physics) , computer science , physics , crystal structure , organic chemistry , catalysis , quantum mechanics , computer network
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 (ΔΛ) and rac (ΔΔ/ΛΛ)}, and between the homochiral (Δ 3 /Λ 3 ) and heterochiral (Δ 2 Λ/Λ 2 Δ) 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(Ru II/III ) orbitals is invoked to explain the IVCT behaviour in the di‐ and trinuclear systems.