Molecular dipole-modulated visible light photoredox reaction over conjugated polymers

Abstract

The molecular dipoles of conjugated polymers (CPs) have a great influence on their intrinsic photophysical properties and are one of the key factors affecting the photocatalytic activity. Therefore, we developed a molecular dipole modulation strategy to regulate the configuration of conjugated polymers by changing the symmetry of the monomer molecules and the electronegativity of the bridging atoms to modulate the magnitude of the in-built electric field (IBEF). The optimized SHOP sample has a significant molecular dipole and thus the highest IBEF, which accelerates the dissociation of excitons into electron-hole pairs and facilitates the photocatalytic redox reaction. In addition, CH4 was the principal output of photocatalytic CO2 reduction by SHOP, producing a maximum yield of 743.4 μmol g−1 and a selectivity of 86.2%. On the other hand, SHOP also efficiently converts isochromane to isochroman-1-one in 96.2% yield, realizing a high economic value conversion of a representative substrate molecule. This proposed strategy offers guidance for designing novel CPs photocatalysts for photoredox reactions.