Das Prasenjit, Chakraborty Gouri, Friese Nico, Roeser Jérôme, Prinz Carsten, Emmerling Franziska, Schmidt Johannes, Thomas Arne
Department of Chemistry/Functional Materials, Technische Universität Berlin, 10623 Berlin, Germany.
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany.
J Am Chem Soc. 2024 Jun 26;146(25):17131-17139. doi: 10.1021/jacs.4c02551. Epub 2024 Jun 14.
Multicomponent reactions (MCRs) offer a platform to create different chemical structures and linkages for highly stable covalent organic frameworks (COFs). As an illustrative example, the multicomponent Povarov reaction generates 2,4-phenylquinoline from aldehydes and amines in the presence of electron-rich alkenes. In this study, we introduce a new domino reaction to generate unprecedented 2,3-phenylquinoline COFs in the presence of epoxystyrene. This work thus presents, for the first time, structural isomeric COFs produced by multicomponent domino and Povarov reactions. Furthermore, 2,3-phenylquinolines can undergo a Scholl reaction to form extended aromatic linkages. With this approach, we synthesize two thermally and chemically stable MCR-COFs and two heteropolyaromatic COFs using both domino and in situ domino and Scholl reactions. The structure and properties of these COFs are compared with the corresponding 2,4-phenylquinoline-linked COF and imine-COF, and their activity toward benzene and cyclohexane sorption and separation is investigated. The position of the pendant phenyl groups within the COF pore plays a crucial role in facilitating the industrially important sorption and separation of benzene over cyclohexane. This study opens a new avenue to construct heteropolyaromatic COFs via MCR reactions.
多组分反应（MCRs）为创建用于高度稳定的共价有机框架（COFs）的不同化学结构和连接方式提供了一个平台。作为一个说明性的例子，多组分Povarov反应在富电子烯烃存在下，由醛和胺生成2,4-苯基喹啉。在本研究中，我们引入了一种新的多米诺反应，在环氧苯乙烯存在下生成前所未有的2,3-苯基喹啉COFs。因此，这项工作首次展示了通过多组分多米诺反应和Povarov反应产生的结构异构COFs。此外，2,3-苯基喹啉可进行肖尔反应以形成扩展的芳族连接。通过这种方法，我们使用多米诺反应以及原位多米诺反应和肖尔反应合成了两种热稳定和化学稳定的MCR-COFs以及两种杂多芳族COFs。将这些COFs的结构和性质与相应的2,4-苯基喹啉连接的COF和亚胺-COF进行了比较，并研究了它们对苯和环己烷吸附及分离的活性。COF孔内侧苯基的位置在促进工业上重要的苯对环己烷的吸附和分离中起着关键作用。这项研究为通过MCR反应构建杂多芳族COFs开辟了一条新途径。
