β-Pyrrole Functionalized Push or Pull Porphyrins: Excited Charge Transfer Promoted Singlet Oxygen Generation

Abstract

Singlet oxygen (1O2) producing photosensitizers are highly sought for developing new photodynamic therapy agents and facilitating 1O2-involved chemical reactions. Often singlet oxygen is produced by the reaction of triplet-excited photosensitizers with dioxygen via an energy transfer mechanism. In the present study, we demonstrate a charge transfer mechanism to produce singlet oxygen involving push or pull functionalized porphyrins. For this, 20 β-pyrrole functionalized porphyrins carrying either an electron-rich push or electron-deficient pull group have been newly synthesized. Photoexcitation of these push-pull porphyrins has been shown to produce high-energy MPδ+-Aδ− or MPδ--Dδ+ charge transfer states. Subsequent charge recombination results in populating the triplet excited states of extended lifetimes in the case of the push group containing porphyrins that eventually react with dioxygen to produce the reactive singlet oxygen of relatively higher quantum yields. The effect of the push and pull groups on the porphyrin periphery in governing initial charge transfer, the population of triplet excited states and their lifetimes, and resulting in improved singlet oxygen quantum yields are systematically probed. The improved performance of 1O2 generation by porphyrins carrying push groups is borne out from this study. © 2023 American Chemical Society.