Behavior of radical ion pairs produced by photoinduced electron transfer in polar solutions

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Abstract The dynamic behavior of radical ion pairs in polar solvents has been studied by directly observing time-resolved transient absorption spectra in the picosecond-hundred nanosecond regime and also by observing the picosecond laser induced photocurrent. Pyrene-N.N-dimethylaniline, pyrene-p-dicy-anobenzene, pyrene-triethylamine exciplex systems and the excited state of pyrene-pyromellitic dian-hydride electron donor-acceptor complexes in polar solvents have been examined. It has been clearly demonstrated that the rate constant kn, of the charge recombination deactivation of radical ion pairs shows a strong dependence upon the energy gap ΔGip, (between the ion pair and the neutral ground state) and upon the molecular nature of individual electron donor or acceptor ions. The plot of knvs ΔGip for the chemically similar π-π exciplex systems as well as singlet excited electron donor-acceptor complex systems studied in this and some previous works showed clearly the characteristic features of the so-called Marcus inverted region.

Journal

  • Tetrahedron

    Tetrahedron 42 6143-6148, 1986-01-01

    Elsevier BV

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