Abstract
The irradiation (λ>520 nm) of a weakly acidic solution containing zinc(II) meso-tetrakis( N- methyl-4-pyridyl)porphine (ZnTMPyP 4+), Fe(bpy) 2+ 3 (bpy≡2,2′-bipyridine) and S 2O 8 2− leads to the formation of the strong one-electron oxidant Fe(bpy) 3 3+ with a quantum yield of about 0.2. The reaction mechanism established by means of flash and steady state photolysis includes photochemical generation of zinc porphyrin radical cation ZnTMPyP ·5+, which rapidly oxidizes Fe(bpy) 3 3+ and ZnTMPyP 4+. After the accumulation of Fe(bpy) 3 3+ in the presence of Co 2+ (oxygen evolution catalyst precursor) an oxygen formation reaction was initiated by means of the addition of KOH (to pH 12) to the solution. O 2 was detected in the gas phase by gas chromatography.
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