Abstract
The competition between electron transfer (ET) and triplet energy transfer (TT) in the quenching of benzophenone, xanthone, and anthraquinone in the triplet state by molecules with both a sufficiently small oxidation potential and low triplet state was investigated in the picosecond to microsecond time scales. In the longer time scale, the product distribution depends strongly on the relative exergonicity of ET and TT processes, the yield of the lower energy product being at least four times larger than that of the other product. Picosecond transient grating measurements reveal that if TT is more exergonic than ET, the TT product is predominantly formed by two sequential ET reactions, i.e., by spin-allowed back ET within the triplet geminate ion pair formed upon ET quenching. However, if ET is more exergonic than TT, no conversion from the TT product to the ET product could be detected. In this case, the product distribution in the microsecond time scale seems to reflect the competition between the two processes. When both processes are exergonic, ET appeared to be always faster than TT. This is in agreement with the severe orbital overlap requirement for TT via the Dexter exchange mechanism.
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