Pyrene‐Alkyne‐Based Conjugated Porous Polymers with Skeleton Distortion‐Mediated •O2‐ and 1O2 Generation for High‐Selectivity Organic Photosynthesis

Abstract Reactive oxygen species (ROS) play a crucial role in determining photocatalytic reaction pathways, intermediate species, and product selectivity. However, research on ROS regulation in polymer photocatalysts is still in its early stages. Herein, we successfully achieved series of modulations to the skeleton of Pyrene‐alkyne‐based (Tetraethynylpyrene (TEPY)) conjugated porous polymers (CPPs) by altering the linkers (1,4‐dibromobenzene (BE), 4,4′‐dibromobiphenyl (IP), and 3,3′‐dibromobiphenyl (BP)). Experiments combined with theoretical calculations indicate that BE‐TEPY exhibits a planar structure with minimal exciton binding energy, which favors exciton dissociation followed by charge transfer with adsorbed O 2 to produce ⋅O 2 − . Thus BE‐TEPY shows optimal photocatalytic activity for phenylboronic acid oxidation and [3+2] cycloaddition. Conversely, the skeleton of BP‐TEPY is significantly distorted. Its planar conjugation decreases, intersystem crossing (ISC) efficiency increases, which makes it more prone for resonance energy transfer to generate 1 O 2 . Therefore, BP‐TEPY displays best photocatalytic activity in [4+2] cycloaddition and thioanisole oxidation. Both above reactant conversion and its product selectivity exceed 99 %. This work systematically reveals the intrinsic structure–activity relationship among the skeleton structure of CPPs, excitonic behavior, and selective generation of ROS, providing new insights for the rational design of highly efficient and selective CPPs photocatalysts.