Precise Regulation in Chain‐Edge Structural Microenvironments of 1D Covalent Organic Frameworks for Photocatalysis

Abstract Covalent organic frameworks (COFs) constitute a promising research topic for photocatalytic reactions, but the rules and conformational relationships of 1D COFs are poorly defined. Herein, the chain edge structure is designed by precise modulation at the atomic level, and the 1D COFs bonded by C, O, and S elements is directionally prepared for oxygen‐tolerant photoinduced electron transfer‐atom transfer radical polymerization (PET‐ATRP) reactions. It is demonstrated that heteroatom‐type chain edge structures (─O─, ─S─) lead to a decrease in intra‐plane conjugation, which restricts the effective transport of photogenerated electrons along the direction of the 1D strip. In contrast, the all‐carbon type chain edge structure (─C─) with higher intra‐plane conjugation not only reduces the energy loss of photoexcited electrons but also enhances the carrier density, which exhibits the optimal photopolymerization performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance.