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Lookup NU author(s): Dr Ben Allen,
Professor Andrew Benniston,
Emeritus Professor Anthony Harriman,
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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.
Author(s): Allen BD, Benniston AC, Harriman A, Mallon LJ, Pariani C
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Print publication date: 01/01/2006
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
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