Rationally Designed Poly(heptazine imide) for Highly Efficient Photoinduced Reversible Deactivation Radical Polymerization

作者：Yefei Ma, Wenjie Zhang, Chengli Wang, Xiaomeng Zhang, Zhe Cui, Peng Fu, Minying Liu, Ge Shi, Xiaoguang Qiao, Beibei Jiang, Yanjie He, Xinchang Pang · 发表于：Macromolecules · 年份：2025 · DOI：10.1021/acs.macromol.5c01232 · 被引用次数：4 · 研究领域：Advanced Photocatalysis Techniques、Advanced Polymer Synthesis and Characterization、Photopolymerization techniques and applications

Polymerization regulated via photocatalysts offers unprecedented spatiotemporal control over reversible deactivation radical polymerization, enabling the preparation of macromolecules with precise molecular weight control and well-defined architectures. Photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization is highly adaptable owing to its wide range of monomer applicability, oxygen tolerance, and mild polymerization conditions. There has been a push to develop innovative photocatalysts with extended light harvesting ability and enhanced photoactivity for the purpose of potential green chemistry. Herein, judiciously designed potassium poly(heptazine imide) (K-PHI) is proposed as a highly effective photocatalyst for oxygen-tolerant PET-RAFT polymerization under visible light. K-PHI is crafted via post-treatment of graphitic carbon nitride (g-C 3 N 4 ) in molten salts, which facilitates the mass transfer and polymerization of melon-based structure. Such post-treatment substantially boosts the crystallinity of K-PHI and imposes a profound impact on photophysical properties and carrier transport efficiency of K-PHI. As a result, structurally optimized K-PHI enables a 16.6-fold increase in photopolymerization rate compared to traditional g-C 3 N 4 while maintaining excellent control features (i.e., low dispersity, high chain-end fidelity, etc.). Furthermore, universal monomer adaptation, general chain transfer agent, and re...