Probing the transition between the localised (Class II) and Localised-to-delocalised (Class II-III) regimes by using intervalence charge-transfer solvatochromism in a series of mixed-valence dinuclear ruthenium complexes


D'Alessandro, D. M., Topley, A. C., Davies, M. S. and Keene, F. R. (2006) Probing the transition between the localised (Class II) and Localised-to-delocalised (Class II-III) regimes by using intervalence charge-transfer solvatochromism in a series of mixed-valence dinuclear ruthenium complexes. Chemistry - a European Journal, 12, (18), 4873-4884. (doi:10.1002/chem.200501483).

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Original Publication URL: http://dx.doi.org/10.1002/chem.200501483

Description/Abstract

Intervalence charge-transfer (IVCT) solvatochromism studies on the diastereoisomeric forms of [{Ru(bpy)(2)}(2)(mu-BL)](5+) (bpy = 2,2'-bipyridine; BL=a series of di-bidentate polypyridyl bridging ligands) reveal that the solvent dependencies of the IVCT transitions decrease as the "tail" of the bridging ligand is extended, and the extent of delocalisation increases. Utilising a classical theoretical approach for the analysis of the intervalence charge-transfer (IVCT) solvatochromism data, the subtle and systematic variation in the electronic properties of the bridging ligands can be correlated with the shift between the localised (class II) and localised-to-delocalised (class II-III) regimes. The investigation of the diastereoisomeric forms of two series of complexes incorporating analogous structurally rigid (fused) and nonrigid (unfused) bridging ligands demonstrates that the differences in the IVCT characteristics of the diastereoisomers of a given complex are accentuated in the latter case, due to a stereochemically induced redox asymmetry contribution. The marked dependence of the IVCT transitions on the stereochemical identity of the complexes provides a quantitative measure of the fundamental contributions of the reorganisational energy and redox asymmetry to the intramolecular electron-transfer barrier at the molecular level.

Item Type: Article
ISSNs: 0947-6539 (print)
Related URLs:
Keywords: chiralty, mixed-valent compounds, ruthenium, solvatochromism polypyridyl bridging ligands, electron-transfer, metal-complexes, electrochemical properties, photophysical properties, osmium(ii) complexes, excited-state, chromatographic-separation, absorption-spectra, exchange reactions
Subjects: Q Science
Q Science > QD Chemistry
Divisions: University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 44414
Date Deposited: 01 Mar 2007
Last Modified: 27 Mar 2014 18:28
URI: http://eprints.soton.ac.uk/id/eprint/44414

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