Redox properties of photoexcited (nBu4N)3PW12O40FeIII porphyrins composite systems

摘要: Abstract The photochemical and photocatalytic properties of (nBu4N)3PW12O40 (PW12O3−40) was investigated in the presence several FeIII-meso-tetrarylporphyrins. excitation polyoxotungstate 2-propanol or cyclohexane leads to its reduction simultaneous oxidation organic substrate. reduced is able, turn, transfer one electron FeIII porphyrin give ferrous complex. In anaerobic cyclohexane, σ-alkyl-FeIII complexes are obtained as a consequence reaction between cyclohexyl radicals iron form. Subsequent oxidative migration σ-bound group from pyrrole nitrogens formation N-substituted porphyrin. results by laser flash photolysis experiments indicate that photoreduced faster than O2. Therefore, photoexcited can operate source electrons for form, thus creating site at which O2 reductively activated. Continuous irradiation composite systems under aerobic conditions cyclohexanol cyclohexanone. comparison with porphyrins alone, photocatalysts present higher yields products. PW12O3−40 they produce amounts hydroxylated product.