Yu Tao-Yuan, Niu Qian, Chen Yifa, Lu Meng, Zhang Mi, Shi Jing-Wen, Liu Jiang, Yan Yong, Li Shun-Li, Lan Ya-Qian
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, PR China.
School of Chemistry, South China Normal University, Guangzhou 510006, PR China.
J Am Chem Soc. 2023 Apr 26;145(16):8860-8870. doi: 10.1021/jacs.2c12313. Epub 2023 Apr 18.
The selective photoisomerization or photocyclization of stilbene to achieve value upgrade is of great significance in industry applications, yet it remains a challenge to accomplish both of them through a one-pot photocatalysis strategy under mild conditions. Here, a sevenfold interpenetrating 3D covalent organic framework () has been synthesized through covalent coupling between ,,,-tetrakis(4-aminophenyl)-1,4-benzenediamine (light absorption and free radical generation) and 5,5'-(2,1,3-benzothiadiazole-4,7-diyl)bis[2-thiophenecarboxaldehyde] (catalytic center). The thus-obtained sevenfold interpenetrating structure presents a functional pore channel with a tunable photocatalytic ability and specific pore confinement effect that can be applied for selective stilbene photoisomerization and photocyclization. Noteworthily, it enables photogeneration of -stilbene or phenanthrene with >99% selectivity by simply changing the gas atmosphere under mild conditions (Ar, Sele. > 99%, Sele. < 1% and O, Sele. < 1%, and Sele. > 99%). Theoretical calculations prove that different gas atmospheres possess varying influences on the energy barriers of reaction intermediates, and the pore confinement effect plays a synergistically catalytic role, thus inducing different product generation. This study might facilitate the exploration of porous crystalline materials in selective photoisomerization and photocyclization.
通过选择性光异构化或光环化实现芪的价值提升在工业应用中具有重要意义，但在温和条件下通过一锅法光催化策略同时实现这两者仍具有挑战性。在此，通过1,4,5,8-四(4-氨基苯基)-1,4-苯二胺（光吸收和自由基生成）与5,5'-(2,1,3-苯并噻二唑-4,7-二基)双[2-噻吩甲醛]（催化中心）之间的共价偶联合成了一种七重互穿三维共价有机框架（）。如此获得的七重互穿结构呈现出具有可调光催化能力和特定孔限域效应的功能性孔道，可用于芪的选择性光异构化和光环化。值得注意的是，通过在温和条件下简单改变气体气氛（Ar，选择性>99%，选择性<1%；O₂，选择性<1%，选择性>99%），它能够以>99%的选择性光生成反式芪或菲。理论计算证明，不同的气体气氛对反应中间体的能垒有不同影响，且孔限域效应起到协同催化作用，从而诱导生成不同产物。该研究可能有助于探索多孔晶体材料在选择性光异构化和光环化方面的应用。
