Photoinduced reactions of covalently linked porphyrin quinones in reversed micelles as studied by EPR spectroscopy

From covalently linked porphyrin quinones, dissolved in reversed micellar solutions, porphyrin radical cations and semiquinone radical anions can be generated photochemically. At pH 7 of the water pool the radical species are rather short-lived and can thus only be observed duringin-situ light irradiation (optical pumping) of the sample. Different polarization patterns are observed in different types of micelles, e.g., CTAB cationic or Triton X-100 neutral reversed micelles. Specifically, in the former absorptive (either Boltzmann relaxed or enhanced absorptive) spectra are obtained, whereas in the latter both species (porphyrin radical cation and semiquinone radical anion) occur in emission. Complete emission is indicative of a strong triplet mechanism.