Photoinduced intramolecular electron transfer reactions within donor-acceptor linked compounds in solution and within donor-acceptor ion-pairs in crystal |
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Authors: | T Ohno K Nozaki A Yoshimura N Ikeda T Iguro |
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Institution: | 1. Chemistry Department, College of General Education, Osaka University, 560, Toyonaka, Osaka, Japan
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Abstract: | Intramolecular electron transfer (ET) processes within donor-acceptor linked compounds in solution and donor-acceptor ion-pairs
in crystal have been investigated by means of laser photolysis kinetic spectroscopy. An excited Ru(II)-moiety of donor-acceptor
compounds undergoes intramolecular electron-transfer to either ruthenium(III) ion, rhodium(III) ion or a cobalt(III) ion,
followed by back ET to regenerate the original reactant. An Arrhenius plot of the ET rate gave a straight line with an intercept
(frequency factor) and a slope (activation energy) for the photoinduced ET and the back ET. Mixed-valence isomer states produced
via photoinitiated ET rapidly decayed via back ET. A common and large frequency factor observed for Ru(II)-Rh(III) compounds is accounted for in terms of solvent-relaxation
dynamics. For the back ET in the Ru(II)-Co(III) compounds, the frequency factors are reduced because of negative entropy change.
ET within donor-acceptor ion-pair of Ru(bpy)23 and Co(CN)36 in crystal took place very rapidly compared with in water. |
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