蒽醌
氰化
共轭微孔聚合物
咔唑
光化学
化学
光催化
有机化学
聚合物
催化作用
作者
Xiaoyun Dong,Yuexin Wang,Fengwei Huang,Xianjun Lang
标识
DOI:10.1016/j.cej.2023.143934
摘要
Conjugated microporous polymers (CMPs), which can be designed through molecular building units, have been widely exploited as photoactive materials. Herein, carbazole and anthraquinone are utilized to prepare a carbazole–anthraquinone CMP (CzAQ-CMP) for visible light photocatalysis. Theoretical calculations suggest hole and electron are located at carbazole and anthraquinone, respectively. Besides, CzAQ-CMP allows for electron transfer to molecular oxygen via anthraquinone, forming superoxide. The hole of CzAQ-CMP drives aerobic oxidative cyanation of N,N-dimethylaniline in methanol. Intriguingly, in the presence of acetic acid, the nucleophilic substitution of trimethylsilyl cyanide by superoxide releases cyanide ion to partake in the α-cyanation of N,N-dimethylaniline. Irradiated by green light, the oxidative cyanation of diverse tertiary amines favorably affords the corresponding α-aminonitriles over CzAQ-CMP in high yields. This work illuminates the rational design of CMPs for photocatalytic selective organic transformations.
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