Pyrazine-based supramolecular photosensitizing assemblies as type I photosensitizers for high-efficiency photooxidation reactions

Donor-acceptor thermally activated delayed fluorescent (TADF) materials have been widely used in photocatalytic reactions as organic photosensitizers. However, the construction of TADF photosensitizers via a supramolecular self-assembly approach with the regulation of reactive oxygen species (ROS) is still a big challenge. In this study, a TADF molecule 4,4'-(6-(pyridin-4-yl)quinoxaline-2,3-diyl)bis(N,N-diphenylaniline) (TPA-PQ) by incorporating triphenylamine (TPA) act as donor and 6-(pyridin-4-yl)quinoxaline (PQ) act as an acceptor was designed and synthesized, which exhibited excellent TADF property and strong intramolecular charge transfer. Meanwhile, the TPA-PQ can not only self-assemble to form nanofiber structure in mixed solvent of H2O and THF, but also can be used as a type I photosensitizer to selectively produce superoxide anion radicals (O2•–). More interestingly, the ROS generated from TPA-PQ can be used as photocatalysts for the oxidative hydroxylation of arylboronic acids and aerobic cross dehydrogenation coupling (CDC) reactions with high yields of 92 % and 88 %, respectively. This study presents an innovative and eco-friendly approach to utilize TADF supramolecular structures for the purpose of conducting photocatalyzed organic reactions. [Display omitted] •A novel donor-acceptor TADF molecule was designed and synthesized.•TPA-PQ can self-assemble to form nanofiber structure in mixed solvent of H2O and THF.•The molecular assemblies of TPA-PQ can be used as a type I photosensitizer to selectively produce superoxide anion radicals.•TPA-PQ assemblies can be used as photocatalysts for the oxidative hydroxylation of arylboronic acids and CDC reactions.