The photocatalytic mechanism of organic dithienophosphole derivatives as highly efficient photo-redox catalysts.

The use of organic photo-redox catalysts to initiate well-controlled photochemical reactions has aroused great interest. The development of visible light-driven photocatalytic reactions, which enable rapid and efficient synthesis of fine products, is highly desired from the perspective of being able to achieve low cost, good reversibility, and environmental friendliness. Herein, the organic photocatalytic cycle, with organic dithienophosphole (DTP) derivatives Ph-DTP and TPA-DTP as the photo-redox catalysts, and iodonium salt (Ar2I+) and ethyl 4-(dimethylamino)benzoate (EDB) as the respective acceptor and donor substrates, is fully analyzed by using density functional theory and dissociative electron transfer theory. We show that the strong redox potentials in the excited state as well as the sufficiently long-lived excited state of both DTP derivatives are a robust driving force for activating the electron acceptor Ar2I+ in the activation process. Moreover, the activation barriers of electron transfer are only 0.43-11.9 kcal mol-1 for the different activation pathways. During the deactivation process, the reaction energy profiles indicate that EDB plays a vital role in reducing DTPs˙+ to their initial states. Importantly, the activation barriers and rate constants in both activation and deactivation processes obtained in this study are better than those of classic Cu-based and metal-free Ph-PTZ-based photo-redox catalysts. The excellent performance of both DTP derivatives thus enables them to be highly efficient organic photo-redox catalysts.