The University of Southampton
University of Southampton Institutional Repository

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

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
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
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.
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
0947-6539
4873-4884
D'Alessandro, Deanna M.
de8b3d62-0504-4bee-836a-084fbb92fcf7
Topley, Amy C.
7ea643ec-c6fe-4510-bc57-f0c0e3f58ef1
Davies, Murray S.
bf015274-0cc2-4403-9827-189d1c32fc81
Keene, F. Richard
d71cb869-3ca7-419e-9f82-26dd07f14eda
D'Alessandro, Deanna M.
de8b3d62-0504-4bee-836a-084fbb92fcf7
Topley, Amy C.
7ea643ec-c6fe-4510-bc57-f0c0e3f58ef1
Davies, Murray S.
bf015274-0cc2-4403-9827-189d1c32fc81
Keene, F. Richard
d71cb869-3ca7-419e-9f82-26dd07f14eda

D'Alessandro, Deanna M., Topley, Amy C., Davies, Murray S. and Keene, F. Richard (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).

Record type: Article

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.

This record has no associated files available for download.

More information

Published date: 5 April 2006
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

Identifiers

Local EPrints ID: 44414
URI: http://eprints.soton.ac.uk/id/eprint/44414
ISSN: 0947-6539
PURE UUID: 1d7af034-7120-4150-9f90-7f86b04e6eaa

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 15 Mar 2024 09:03

Export record

Altmetrics

Contributors

Author: Deanna M. D'Alessandro
Author: Amy C. Topley
Author: Murray S. Davies
Author: F. Richard Keene

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×