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A new aspect of photoinduced electron transfer in acetonitrile

1992; Elsevier BV; Volume: 65; Issue: 1-2 Linguagem: Inglês

10.1016/1010-6030(92)85039-w

1873-2666

Kôichi Kikuchi,

Advanced Chemical Physics Studies

Four kinds of evidence for exciplex formation in acetonitrile are summarized. They indicate that the fluorescence quenching mechanism of an electron donor-acceptor system depends on (i) effective quenching distance and (ii) free-enthalpy change of actual electron transfer in addition to (iii) solvent polarity. It is shown that the Rehm-Weller relationship (and the lack of an inverted region in it) is interpreted by taking into account both (i) and (ii). A criterion for determining the quenching mechanism in a highly exothermic region is proposed.