Designed polymeric conjugation motivates tunable activation of molecular oxygen in heterogeneous organic photosynthesis

• 作者: Wenhao Sun Yonggang Xiang Zhihui Jiang Shengyao Wang Nan Yang Shangbin Jin Linhao Sun Huailong Teng Hao Chen
• 来源期刊: 科学通报（英文版）
• 年，卷（期）: 2022,（1）
• 所属期刊栏目: Physical Sciences
• 页码范围: 61-70
• 页数: 10页
• 语种: 英文

摘要

Photocatalytic oxidative organic reactions are important synthetic transformations,and research on reac-tion 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 molec-ular oxygen activation induced by polymeric conjugation in nonmetallic conjugated microporous poly-mers (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 oxi-dation of sulfides and the dehydrogenative coupling of amines,and could provide insight into the rational design of CMPs for various heterogeneous organic photosynthesis.