Restricted Growth of Vinylene-Linked Covalent Organic Frameworks along Two-Dimensional Plane Using Heterogeneous Catalysis

• DOI: 10.1021/jacs.4c01836
• Publication Date: 2024-08-06T21:18:36Z
• Authors: Yuan-Zhe Cheng; Dong-Hui Yang; Wenyan Ji; Peng-Yuan Hao; Pengtao Ma; Jingping Wang; Jingyang Niu; Xuesong Ding; Lizhi Zhang; Bao-Hang Han
• Keywords: Trifluoroacetic acid

The vinylene-linked covalent organic frameworks (viCOFs) have been generally synthesized in the presence of homogeneous catalysts such as KOH or trifluoroacetic acid. However, highly ordered viCOFs cannot always be obtained due to uncommitted growth viCOF layers system with ubiquitous catalysts. Here, we propose a scalable protocol restrict along two-dimensional (2D) plane by introducing heterogeneous catalyst, polyoxometalates (POMs). With unique Brønsted alkalinity and catalytic surface, POMs induce 2D surface substrate restrain generation out-of-plane branches. Based on this protocol, six typical high crystallinity porosity were within shorter reaction time compared reported works using common for synthesis. On basis density functional theory calculations experimental results, bottom intercalation pattern was revealed during reaction. greatly promotes orderly assembly monomers, thus shortening improving viCOFs. Furthermore, catalysis strategy is suitable gram-scale preparation These results provide novel avenue synthesis high-quality may bring new insights into synthetic methodology COFs.