Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H2O2 Production and Organic Synthesis

While being important candidate for heterogeneous photocatalyst, conjugated polymer typically exhibits random charge transfers between the alternating donor and acceptor units, which severely limits its catalytic efficiency. Herein, inspired by natural photosystem, the concept of guiding the charge migration to specific reaction sites is employed to significantly boost photocatalytic performance of linear conjugated polymers (LCPs) with pendant functional groups via creating programmed charge-transfer channels from the backbone to its pendant moiety. The pendant benzothiadiazole, as revealed in both in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations, can act as electron "reservoir" that aggregates electrons at the active sites. Moreover, the presence of charge-transfer channels, evidenced by transient absorption spectroscopy (TAS), accelerates the electron transfer, preventing the recombination of electrons and holes. As a result, in this elaborately-designed architecture, the photogenerated electron can move smoothly towards the reduction sites, facilitating the reduction of O