Pachfule Pradip, Acharjya Amitava, Roeser Jérôme, Sivasankaran Ramesh P, Ye Meng-Yang, Brückner Angelika, Schmidt Johannes, Thomas Arne
Department of Chemistry/Functional Materials , Technische Universität Berlin , Hardenbergstraße 40 , 10623 Berlin , Germany . Email:
Leibniz Institute for Catalysis , University of Rostock , Albert-Einstein-Str. 29a , 18059 Rostock , Germany.
Chem Sci. 2019 Aug 5;10(36):8316-8322. doi: 10.1039/c9sc02601k. eCollection 2019 Sep 28.
Covalent organic frameworks (COFs) are promising materials for applications in photocatalysis, due to their conjugated, porous and chemically stable architectures. Alternating electron donor-acceptor-type structures are known to enhance charge carrier transport mobility and stability in polymers and are therefore also interesting building units for COFs used as photocatalysts but also as photoinitiator. In this work, two donor-acceptor COFs using electron deficient 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-]thiophene-2,5-dicarbaldehyde or [2,2'-bithiophene]-5,5'-dicarbaldehyde linkers are presented. The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA). These results pave the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light.
共价有机框架（COFs）因其共轭、多孔且化学稳定的结构，是在光催化领域具有应用前景的材料。已知交替的电子供体-受体型结构可增强聚合物中电荷载流子的传输迁移率和稳定性，因此也是用作光催化剂以及光引发剂的COFs的有趣构建单元。在这项工作中，展示了两种供体-受体型COFs，它们使用缺电子的4,4',4''-(1,3,5-三嗪-2,4,6-三基)三苯胺以及富电子的基于噻吩的噻吩并[3,2-b]噻吩-2,5-二甲醛或[2,2'-联噻吩]-5,5'-二甲醛连接体。所得的结晶且多孔的COFs已被用作光引发剂，用于甲基丙烯酸甲酯（MMA）在可见光诱导下自由基聚合成聚甲基丙烯酸甲酯（PMMA）。这些结果为开发强大的多相光化学体系铺平了道路，该体系可实现可见光诱导的自由基转移。
