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) 32 and Co(CN) 63 in crystal took place very rapidly compared with in water.
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Ohno, T., Nozaki, K., Yoshimura, A. et al. Photoinduced intramolecular electron transfer reactions within donor-acceptor linked compounds in solution and within donor-acceptor ion-pairs in crystal. Res Chem Intermed 20, 807–814 (1994). https://doi.org/10.1163/156856794X00559
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DOI: https://doi.org/10.1163/156856794X00559