Resonance Raman and electronic absorption studies of iron protoporphyrin IX chloride (hemin) in non-ionic Triton X-100 micelle in the absence and presence of hindered imidazole (2-methylimidazole and 1,2-dimethylimidazole) and unhindered imidazole under various experimental conditions are reported. Hemin undergoes photoreduction at the metal center, both in the absence and presence of hindered imidazole, in anaerobic, alkaline and neutral pH conditions on photoexcitation by laser radiation at 441.6 and 457.9 nm. It is inferred from this study that only the monomer hemin encapsulated within the micelle under the alkaline pH conditions is photoreducible. The photoreduction of hemin in this micelle occurs from an electron transfer as a result of dissociation of coordinated hydroxyl ion to the iron atom in the photoexcited state, which may also involve the OH ! Fe charge transfer transition around 360 nm.
We report the formation and characterization of
(oxoferryl)tetraphenylporphyrin ((TPP)FeIVO)
as a result of
photodisproportionation of the μ-oxo dimer,
(Fe(TPP))2O, obtained on solubilization of
Fe(TPP)Cl in an aqueous
alkaline TX-100 detergent micelle, under 441.6 nm laser excitation at
room temperature and at −50 °C. The
other photoproduct is identified as a five-coordinated, high-spin
(5cHS) ferrous complex.
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