Photocatalytic oxidative organic reactions are important synthetic transformations, and research on reaction selectivity by reactive oxygen species (ROS) is significant. To date, however, there has rarely been any focus on the directed generation of ROSs. Herein, we report the first identification of tunable molecular oxygen activation induced by polymeric conjugation in nonmetallic conjugated microporous polymers (CMP). The conjugation between these can be achieved by the introduction of alkynyl groups. CMP-A with an alkynyl bridge facilitates the intramolecular charge mobility while CMP-D, lacking an alkynyl group enhances the photoexcited carrier build-up on the surface from diffusion. These different processes dominate the directed ROS generation of the superoxide radical (O₂⁻) and singlet oxygen (¹O₂), respectively. This theory is substantiated by the different performances of these CMPs in the aerobic oxidation of sulfides and the dehydrogenative coupling of amines, and could provide insight into the rational design of CMPs for various heterogeneous organic photosynthesis.

光催化氧化有机反应是重要的合成转化，活性氧（ROS）对反应选择性的研究具有重要意义。然而，迄今为止，很少有人关注 ROS 的定向生成。在此，我们报告了非金属共轭微孔聚合物 (CMP) 中聚合物共轭诱导的可调分子氧活化的首次鉴定。这些之间的共轭可以通过引入炔基来实现。带有炔基桥的 CMP-A 促进了分子内电荷迁移，而缺少炔基的 CMP-D 增强了光激发载流子在扩散过程中在表面上的积累。这些不同的过程主导了超氧自由基 ( O ₂ ^-) 和单线态氧 ( ¹ O ₂ ), 分别。这些 CMP 在硫化物的有氧氧化和胺的脱氢偶联中的不同性能证实了这一理论，并且可以为各种异相有机光合作用的 CMP 的合理设计提供见解。