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 ...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(·O_(2)^(-))and singlet oxygen(^(1)O_(2)),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.展开更多
基金supported by the National Natural Science Foundation of China(51902121,52073110,22071072,51872107,21975090,and 21801086)the Fundamental Research Funds for the Central Universities of China(2662018QD011,2662018PY052,and 2662019PY023)the Natural Science Foundation of Hubei Province(2019CFB322)。
文摘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(·O_(2)^(-))and singlet oxygen(^(1)O_(2)),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.
