Covalent organic frameworks (COFs) are ideal heterogeneous photocatalytic platforms offering fascinating spaces for manipulation given their clearly defined structures along with pre-customizable skeletons. Herein, an imine-based COF Im-oMe featuring N and O sites allowing the integration of CuII ions via coordination bonds in local regions of the skeleton is reported for aerobic photoinduced electron/energy transfer atom transfer radical polymerization (PET-ATRP) in the aqueous phase. CuII@Im-oMe of anchored CuII ions is capable of triggering skeleton localized polarization effects, producing greater dipole moment driving force and facilitating the charge separation and transport to enhance its photopolymerization performance. Meanwhile, the system does not require additional addition of transition metal halides, and remains highly active after 3 cycles. The present work expands the feasible design methods and strategies of heterogeneous photocatalysts available for precision production of polymers in open-air environments.

中文翻译：

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铜(II)离子配位共价有机骨架诱导好氧PET-ATRP在水相中的原位电荷极化效应


共价有机框架（COF）是理想的异质光催化平台，由于其明确定义的结构和预先定制的骨架，提供了令人着迷的操作空间。在此，报道了一种基于亚胺的 COF Im-oMe，具有 N 和 O 位点，允许通过骨架局部区域的配位键整合 CuII 离子，用于有氧光诱导电子/能量转移原子转移自由基聚合 (PET-ATRP)。水相。锚定CuII离子的CuII@Im-oMe能够触发骨架局域极化效应，产生更大的偶极矩驱动力，促进电荷分离和传输，从而增强其光聚合性能。同时，该体系不需要额外添加过渡金属卤化物，并且在3个循环后仍然保持高活性。目前的工作扩展了可用于在露天环境中精密生产聚合物的异质光催化剂的可行设计方法和策略。