2D (two-dimensional) covalent organic frameworks (COFs) have recently emerged as versatile photoactive functional materials. Herein, three β-ketoenamine linked 2D COFs were assembled with 2,4,6-triformylphloroglucinol (Tp) and 4,7-bis(4-aminophenyl)-2,1,3-benzothiadiazole (BTD) as the building blocks at 150, 120, and 25 ℃ respectively, leading to Tp-BTD-150, Tp-BTD-120, and Tp-BTD-25. In particular, the facile synthesis at 25 ℃ afforded Tp-BTD-25 that featured superior activity for the photocatalytic selective aerobic oxidation of benzylamine to the other two assembled at higher temperatures. Most importantly, both the stability and activity of Tp-BTD-25 photocatalyst were augmented with exogenous 5 mol% TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) to ease the transfer of electrons and protons during the oxidation of benzyl amines. Preeminently, the selective aerobic oxidation of benzyl amines into imines was established by cooperative photocatalysis of Tp-BTD-25 with TEMPO irradiated by blue LEDs (light-emitting diodes). This work underscores that crystalline 2D COFs via facile synthesis can cooperatively work with a redox mediator to steer photocatalytic selective reactions.

二维（二维）共价有机框架（COF）最近已成为通用的光活性功能材料。在此，三个 β-酮烯胺连接的二维 COF 与 2,4,6-三甲酰基间苯三酚 (Tp) 和 4,7-双(4-氨基苯基)-2,1,3-苯并噻二唑 (BTD) 作为构建单元在 150 、120 和 25 ℃ 分别导致 Tp-BTD-150、Tp-BTD-120 和 Tp-BTD-25。特别是，在 25 ℃ 下的简便合成提供了 Tp-BTD-25，其具有优异的光催化选择性将苄胺氧化成其他两种在更高温度下组装的活性。最重要的是，Tp-BTD-25 光催化剂的稳定性和活性都通过外源性 5 mol% TEMPO（2,2,6,6-四甲基哌啶-N-oxyl) 以在苄胺氧化过程中促进电子和质子的转移。最重要的是，苄胺选择性有氧氧化成亚胺是通过 Tp-BTD-25 与蓝色 LED（发光二极管）照射的 TEMPO 的协同光催化作用建立的。这项工作强调了通过简单合成的结晶 2D COF 可以与氧化还原介质协同工作以引导光催化选择性反应。