Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(II) complex

The catalytic durability of an organic photocatalyst, 9-mesityl-10-methyl acridinium ion (Acr+–Mes), has been dramatically improved by the addition of [{tris(2-pyridylmethyl)amine}CuII](ClO4)2 ([(tmpa)CuII]2+) in the photocatalytic oxygenation of p-xylene by molecular oxygen in acetonitrile. Such an improvement is not observed by the addition of Cu(ClO4)2 in the absence of organic ligands. The addition of [(tmpa)Cu]2+ in the reaction solution resulted in more than an 11 times higher turnover number (TON) compared with the TON obtained without [(tmpa)CuII]2+. In the photocatalytic oxygenation, a stoichiometric amount of H2O2 formation was observed in the absence of [(tmpa)CuII]2+, however, much less H2O2 formation was observed in the presence of [(tmpa)CuII]2+. The photocatalytic mechanism was investigated by laser flash photolysis measurements in order to detect intermediates. The reaction of O2˙− with [(tmpa)CuII]2+ monitored by UV-vis spectroscopy in propionitrile at 203 K suggested formation of [{(tmpa)CuII}2O2]2+, a transformation which is crucial for the overall 4-electron reduction of molecular O2 to water, and a key in the observed improvement in the catalytic durability of Acr+–Mes.