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3D Covalent Organic Frameworks with 16-Connectivity for Photocatalytic C(sp 3 )-C(sp 2 ) Cross-Coupling.

Meng LuShuai-Bing ZhangRun-Han LiLong-Zhang DongMing-Yi YangPei HuangYu-Fei LiuZe-Hui LiHan ZhangMi ZhangShun-Li LiYa-Qian Lan
Published in: Journal of the American Chemical Society (2024)
The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher connectivity remains a great challenge in the field of COF structural design. Herein, this work reports a hierarchical expansion strategy for making 16-connected building blocks to construct 3D COFs with sqc topology. The [16 + 2] construction achieved by condensation between a 16-connected carbazolyl dicyanobenzene-based building block (CzTPN) and linear diamino linkers (BD or Bpy) affords two 3D COFs (named CzBD COF and CzBpy COF). Furthermore, attributed to the well-organized donor-acceptor (D-A) heterojunction, the Ni chelated CzBpy COF (Ni@CzBpy COF) exhibits excellent performance for photoredox/Ni dual catalytic C(sp 3 )-C(sp 2 ) cross-coupling of alkyltrifluoroborates with aryl halides, achieving a maximum 98% conversion and 94% yield for various substrates. This work developed the first case of high-connectivity COFs bearing 16-connected units, which is the highest connectivity reported until now, and achieved efficient photocatalysis applications, thus greatly enriching the possibilities of COFs.
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