Wu Bang, Jiang Xinyue, Liu Yang, Li Qiu-Yan, Zhao Xinsheng, Wang Xiao-Jun
Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal University Xuzhou 221116 P. R. China
School of Physics and Electronic Engineering, Jiangsu Normal University Xuzhou 221116 P. R. China.
RSC Adv. 2021 Oct 14;11(53):33653-33660. doi: 10.1039/d1ra06118f. eCollection 2021 Oct 8.
Porous organic polymers (POPs), owing to their abundant porosity, high stability and well-tunable properties, are promising candidates as heterogeneous photocatalysts for organic transformations. Here we report two vinylene-bridged donor-acceptor (D-A) structural POPs (TpTc-POP and TbTc-POP) that are facilely constructed by the electron-rich triarylamine and electron-deficient tricyanomesitylene as key building blocks by the organic base catalyzed Knoevenagel condensation. Both TpTc-POP and TbTc-POP possess hierarchical meso- and micro-pores with a high surface area. Furthermore, the unsubstituted vinylene linkages of D-A moieties in their polymer backbones extend their π-conjugation and render their broad absorption range in the visible-light region. Thus, these DA-POPs exhibited highly effective photocatalytic activities for aerobic oxidative coupling of amines to imines under visible light irradiation. This study shows the great potential of conjugated POPs with a D-A structural feature in designing highly efficient and active heterogeneous photocatalytic systems.
多孔有机聚合物（POPs）因其丰富的孔隙率、高稳定性和良好的可调性，有望成为用于有机转化的非均相光催化剂。在此，我们报道了两种亚乙烯基桥连的供体-受体（D-A）结构的POPs（TpTc-POP和TbTc-POP），它们由富电子的三芳基胺和缺电子的三氰基均三甲苯作为关键结构单元，通过有机碱催化的Knoevenagel缩合反应简便地构建而成。TpTc-POP和TbTc-POP均具有分级的介孔和微孔，且比表面积高。此外，它们聚合物主链中D-A部分的未取代亚乙烯基键扩展了其π共轭，使其在可见光区域具有宽吸收范围。因此，这些DA-POPs在可见光照射下对胺有氧氧化偶联生成亚胺表现出高效的光催化活性。这项研究表明，具有D-A结构特征的共轭POPs在设计高效、活性的非均相光催化体系方面具有巨大潜力。
