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Reduction of Triplet Tetraphenyl-Prophyrin Dication By Aryl Amines and Hydroquinones: Kinetics and Primary Radical Yields

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The photophysics and one-electron reduction oftriplet tetraphenylporphyrin dication by homologous series of substituted triphenylamines and hydroquinones in acetone solution have been studied by nanosecond flash photolysis. Triplet yield is -0.3 and direct internal conversion from the singlet is a major decay pathway. Quenching rates (109 - 106 M-1 s-1) for reductants covering a range of ΔG0' -0.4 V lead to reorganization energies λ ~0.6 ±0.1 eV. Radical yields (~0.38 for the amines) are remarkably constant for recombination free energies between 1.02 and 1.45 V. A rate-limiting step in the back reaction is suggested, involving spin-orbit relaxation of the primary radical pair.

Affiliations: 1: Department of Chemistry, Brandeis University, Waltham, MA 02254-9110, U.S.A.; 2: Department of Chemistry, University of Illinois at Chicago, Box 4348, Chicago, IL 60680, U.S.A.

10.1163/156856794X00306
/content/journals/10.1163/156856794x00306
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/content/journals/10.1163/156856794x00306
1994-01-01
2016-12-09

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