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| - Excited Singlet State Reactions of Triphenylpyrylium Ion with Electron Donors: Evidencefor Electron Transfer and the Observation of Marcus Inverted Region for the Charge Shiftin the Radical Pair
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| - The excited singlet state of 2,4,6-triphenylpyryliumion reacts with benzene derivatives by the electrontransfermechanism, and the radical yield was measured using the flashphotolysis technique. A poor correlation isobserved between experimental and theoretical kqvalues calculated using kd from the Debyeexpression.The observed quenching constants are in good agreement with thekq values calculated usingkd = 3.7 × 1010M-1 s-1, which isobtained from Smoluchowski expression andΔG⧧ from the Rehm−Wellerexpression.The back electron transfer rate constant is determined from thequantum yield of the radical. Marcus invertedregion is observed for the back electron transfer rate constants in thehighly exothermic region of ΔGb.
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