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

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 (& horbar;O & horbar;, & horbar;S & horbar;) 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 (& horbar;C & horbar;) 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. 1D Covalent organic frameworks (COFs) with sql topology matches to non-linear C2 and D2h building blocks are fabricated. All-carbon compared to hybrid-atom-containing chain edge structures can increase carrier density, more effectively mitigate thermal relaxation phenomenon, reduce the energy loss of photoexcited electrons, and realize more effective in-plane transport of photoexcited electrons for enhanced oxygen-tolerant photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) performance. image