Electron and energy transfer within dyads involving polypyridylruthenium(II) and -osmium(II) centres separated by rigid alicyclic bridges
Kelso, Laurence S., Smith, Trevor A., Schlutz, Austin C., Junk, Peter C., Warrener, Ronald N., Ghiggino, Kenneth P., and Keene, F. Richard (2000) Electron and energy transfer within dyads involving polypyridylruthenium(II) and -osmium(II) centres separated by rigid alicyclic bridges. Dalton Transactions, 2000 (15). pp. 2599-2606.
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View at Publisher Website: http://dx.doi.org/10.1039/b003174g
Rigid alicyclic frameworks (often referred to as molracs, relating to the molecular rack nature of the frame) have been used to vary the separation between organic electron-acceptor (quinone) moieties and chromophoric polypyridylruthenium(II) centres, and between metal centres in Ru–Ru and Ru–Os dinuclear complexes. Photophysical studies have allowed a preliminary insight into the effectiveness of such alicyclic structures in mediating intramolecular photoinduced energy and electron transfer. In the chromophore–spacer–quinone dyads, solvent-dependent quenching of the ruthenium(II) MLCT emission was observed and attributed to electron transfer processes. Distance and stereochemical dependencies of the quenching suggested that through-bond coupling was a factor in these systems. In the heterodinuclear systems, the photo-excited ruthenium(II) chromophore underwent intramolecular energy transfer to the osmium(II) component. A through-space Förster dipole–dipole mechanism could adequately account for the rate of the energy transfer process observed.
|Item Type:||Article (Refereed Research - C1)|
|Keywords:||electron transfer; energy transfer; dinuclear; ruthenium; osmium; molrac; distance|
|FoR Codes:||03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%|
|SEO Codes:||97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%|
|Deposited On:||18 Feb 2010 11:05|
|Last Modified:||07 Dec 2012 16:21|
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