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Journal of Chemical Sciences

, Volume 105, Issue 6, pp 495–503 | Cite as

Photoinduced ET and back-ET in bimetallated compounds of Ru(II)-Rh(III) and Ru(II)-Co(III)

  • K. Nozaki
  • A. Yoshimura
  • T. Ohno
Special Issue on Solar Energy and Applied Photochemistry

Abstract

Intramolecular electron transfer processes in bimetallated donor-acceptor compounds have been investigated by means of laser photolysis kinetic spectroscopy. An excited Ru(II)-moiety of donor-acceptor compounds undergoes intramolecular electrontransfer to either a rhodium(III) ion or a cobalt(III) ion, followed by back-electron transfer, an Arrhenius plot of the electron-transfer-rate gave a straight line of intercept (frequency factor) and slope (activation energy) for the photoinduced electron transfers and the back electron transfers. A common and large frequency factor observed for Ru(H)-Rh(III) compounds is accounted for in terms of solvent-relaxation dynamics. The activation energy observed consists of outersphere rearrangement energy depending on the metal ion-metal ion distance. For the photoinduced electron transfers and subsequent back-electron transfers in the Ru(II)-Co(III) compounds, the electron-transfer-rates are reduced because of weak electronic coupling, large rearrangement energy and negative entropy change.

Keywords

Donor-acceptor linked compound electron transfer nuclear tunnelling temperature-dependence of ET rate rearrangement energy 

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Copyright information

© Indian Academy of Sciences 1993

Authors and Affiliations

  • K. Nozaki
    • 1
  • A. Yoshimura
    • 1
  • T. Ohno
    • 1
  1. 1.Chemistry Department, College of General EducationOsaka UniversityToyonaka, OsakaJapan

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