Supramolecular system composed of B-12 model complex and organic photosensitizer: impact of the corrin framework of B-12 on the visible- light- driven dechlorination without the use of noble metals

摘要

The visible-light-driven dechlorination system without the use of a noble metal has been developed. We screened the combination of cobalt catalysts having square-planar monoanionic ligands (hydrophobic B-12 model complex 1/imine-oxime type complex 2) and typical red dyes (Rose Bengal 3/Rhodamine B 4/Nile Red 5) for the construction of a dehalogenation system via a noble-metal-free and visible-light-driven process. The combination of the hydrophobic B-12 model complex 1 and Rose Bengal 3 exhibited the highest catalytic activity to 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) to form the monodechlorinated compound, 1,1-bis(4-chlorophenyl)-2,2-dichloroethane, as the major product. The prolonged photocatalysis of DDT by the B-12-Rose Bengal system afforded the tri-dechlorinated compound, trans-4,4-dichlorostilbene, as the major product. Furthermore, we investigated the mechanism of the dehalogenation cycle using various methods such as UV-vis spectroscopy and laser flash photolysis. Finally, we clarified the advantage of using the hydrophobic B-12 model complex 1 as an electron acceptor as well as a cobalt catalyst in the organic dye-involved photocatalysis.