The synthesis of covalent organic frameworks (COFs) at bulk scale require robust, straightforward, and cost‐effective techniques. However, the traditional solvothermal synthetic methods of COFs suffer low scalability as well as requirement of sensitive reaction environment and multiday reaction time (2‐10 days) which greatly restricts their practical application. Here, we report microwave assisted rapid and optimized synthesis of a donor‐acceptor (D−A) based highly crystalline COF, TzPm‐COF in second (10 sec) to minute (10 min) time scale. With the increasing of the time from seconds to minutes crystallinity, porosity and morphological changes are also observed for TzPm‐COF. Owing to visible range light absorption, suitable band alignment, and low exciton binding energy (Eb=64.6 meV), TzPm‐COF can efficaciously produce superoxide radical anion (O2•−) after activating molecular oxygen (O2) which eventually drives aerobic photooxidative amidation reaction with high recyclability. This photocatalytic approach works well with a variety of substituted aromatic aldehydes having electron‐withdrawing or donating groups and cyclic, acyclic, primary or secondary amines with moderate to high yield. Furthermore, catalytic mechanism was established by monitoring the real‐time reaction progress through in‐situ diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) study.

中文翻译：

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微波辅助快速合成光氧化酰胺化催化供体-受体共价有机框架

大规模合成共价有机框架（COF）需要稳健、简单且经济高效的技术。然而，传统的COFs溶剂热合成方法的可扩展性较低，并且需要敏感的反应环境和多天的反应时间（2-10天），极大地限制了其实际应用。在这里，我们报告了微波辅助快速优化合成基于供体-受体（DA）的高度结晶COF，TzPm-COF，时间范围为秒（10秒）到分钟（10分钟）。随着时间从几秒增加到几分钟，TzPm-COF 也观察到结晶度、孔隙率和形态变化。由于可见光吸收、合适的能带排列和低激子结合能（Eb=64.6 meV），TzPm-COF在激活分子氧（O2）后可以有效地产生超氧自由基阴离子（O2•−），最终驱动有氧光氧化酰胺化反应具有较高的可回收性。这种光催化方法适用于各种具有吸电子或供电子基团的取代芳香醛以及环状、无环、伯胺或仲胺，具有中等到高产率。此外，通过原位漫反射红外傅里叶变换光谱（DRIFTS）研究监测实时反应进程，建立了催化机制。