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Formation of Photochemical π-Cation Radicals I. μ-Oxo-Iron (Iii) Tetraphenylporphyrin

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We have monitored the spectra and kinetics of μ-oxo iron (III) tetraphenyl porphyrin. The spectral changes between 460 nm and 770 nm were observed after excitation with 25 ps fwhm, 355 nm pulse. Kinetic studies from -100 ps to 4 ns suggest that after the immediate formation of the excited states a transient species is formed which we assign to the π-cation radical-ferrous porphyrin pair. This pair decays with a time constant of 600 ps ± 100 ps leaving a small amount of disproportionation reaction photoproducts. The spectra and kinetics of the transients, were not altered by concentration (0.15 OD - 1.0 OD at 571 nm), solvent or addition of oxygen.

Affiliations: 1: Department of Chemistry University of California, Irvine Irvine, California U.S.A., 92717; 2: Veterans Administration Medical Center and University of Arkansas for Medical Sciences Little Rock, Arkansas U.S.A., 72205


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