Regulation of Exciton Effects in Functionalized Conjugated Polymers by B‐N Lewis Pairs for Visible‐Light Photocatalysis

Abstract Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far‐reaching in facilitating photocatalysis. A series of B−N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B−N Lewis pairs can dramatically increase the distance of charge transfer ( D index) and the amount of electron transfer and reduce the Coulomb attraction energy ( E C ), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free‐charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.