We investigated the consecutive photoinduced electron transfer (conPET) mechanism that has been proposed to operate with PDI•– as photocatalyst to reduce 4-bromoacetophenone (BAP), using two strategies based on pump-pump-probe spectroscopy. Our results reveal that the quenching of PDI•–* by BAP occurs only in the static regime, that allows for a large electronic coupling. Such quenching does not require any pre-association of the reactants and is simply enabled by the large quencher concentrations. However, because of the large electronic coupling, the quenching product recombines too quickly for the reduced BAP to undergo any useful follow-up reaction. Further information can be found in a just published Open Access article in Chemical Science (10.1039/D6SC02462A). The figures are reproduced under C.C. 3.0 License.
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Eric Vauthey
Physical Chemistry Department - Sciences II - University of Geneva
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