Photoelectron detachment and solvated electron dynamics of the Cobalt(III) and Iron(III) oxalato complexes
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The photochemical redox reaction kinetics of [M(III)(C 2O 4)S 3] 3- [M = Co, Fe] complexes have been reexamined and studied by time-resolved spectroscopy. The redox mechanisms of the two systems, Co and Fe, were found to be similar to each other, and solvated electrons were observed immediately after 266/267 nm photoexcitation. A reaction mechanism is proposed that involves photoelectron detachment as a primary process. The charge-transfer bands for both complexes, which had been attributed to ligand to metal charge-transfer (LMCT) transitions previously, are reassigned to charge transfer to solvent (CTTS) transitions. 2007 American Chemical Society.