A Fully Coplanar Donor–Acceptor Polymeric Semiconductor with Promoted Charge Separation Kinetics for Photochemistry

Abstract Charge generation and separation are regarded as the major constraints limiting the photocatalytic activity of polymeric photocatalysts. Herein, two new linear polyarylether‐based polymers (PAE–CPs) with distinct linking patterns between their donor and acceptor motifs were tailor‐made to investigate the influence of different linking patterns on the charge generation and separation process. Theoretical and experimental results revealed that compared to the traditional single‐stranded linker, the double‐stranded linking pattern strengthens donor–acceptor interactions in PAE–CPs and generates a coplanar structure, facilitating charge generation and separation, and enabling red‐shifted light absorption. With these prominent advantages, the PAE–CP interlinked with a double‐stranded linker exhibits markedly enhanced photocatalytic activity compared to that of its single‐strand‐linked analogue. Such findings can facilitate the rational design and modification of organic semiconductors for charge‐induced reactions.