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Competing through-space and through-bond, intramolecular triplet-energy transfer in a supposedly rigid ruthenium(II) tris(2,2′-bipyridine)- fullerene molecular dyad

Lookup NU author(s): Dr Ben Allen, Professor Andrew Benniston, Emeritus Professor Anthony Harriman, Laura Wildsmith, Consuelo Pariani

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Abstract

A ditopic ruthenium(II) tris(2,2′-bipyridyl)-based fullerene conjugate has been synthesized so as to separate the photoactive terminals by way of a short ethynylene spacer group that is expected to act as a rigid rod. Intramolecular triplet-energy transfer from the metal complex to the fullerene is quantitative at all temperatures and there is no indication for competing electron transfer. Temperature dependence studies indicate two pathways for triplet-energy transfer. An activationless route dominates at low temperature and is attributed to through-bond electron exchange that takes place via super-exchange interactions. The triplet energy of the bridging unit lies well above that of the metal complex. An activated process is switched-on at high temperatures and is believed to involve through-space electron exchange within closed conformations. Molecular dynamics simulations predict that, in addition to an extended conformation, the linker can distort in such a way that the terminals come into orbital contact. In fact, the resultant closed conformation possesses an idealised geometry for fast electron exchange. © the Owner Societies 2006.


Publication metadata

Author(s): Allen BD, Benniston AC, Harriman A, Mallon LJ, Pariani C

Publication type: Article

Publication status: Published

Journal: Physical Chemistry Chemical Physics

Year: 2006

Volume: 8

Issue: 35

Pages: 4112-4118

Print publication date: 01/01/2006

ISSN (print): 1463-9076

ISSN (electronic): 1463-9084

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b609080j

DOI: 10.1039/b609080j


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