Unveiling upsurge of photogenerated ROS: control of intersystem crossing through tuning aggregation patterns

Chem Sci. 2022 Dec 12;14(2):323-330. doi: 10.1039/d2sc06445f. eCollection 2023 Jan 4.

Abstract

Photo-induced reactive oxygen species (ROS) generation by organic photosensitizers (PSs), which show potential in significant fields such as photodynamic therapy (PDT), are highly dependent on the formation of the excited triplet state through intersystem crossing (ISC). The current research on ISC of organic PSs generally focuses on molecular structure optimization. In this manuscript, the influence of aggregation patterns on ISC was investigated by constructing homologous monomers (S-TPA-PI and L-TPA-PI) and their homologous dimers (S-2TPA-2PI and L-2TPA-2PI). In contrast to J-aggregated S-TPA-PI, S-2TPA-2PI-aggregate forming "end-to-end" stacking through π-π interaction could generate ROS more efficiently, due to a prolonged exciton lifetime and enhanced ISC rate constant (k ISC), which were revealed by femtosecond transient absorption spectroscopy and theoretical calculations. This finding was further validated by the regulation of aggregation patterns induced by host-guest interaction. Moreover, S-2TPA-2PI could target mitochondria and achieve rapid mitophagy to cause more significant cancer cell suppression. Overall, the delicate supramolecular dimerization tactics not only revealed the structure-property relationship of organic PSs but also shed light on the development of a universal strategy in future PDT and photocatalysis fields.