Bottom‐Up Construction of Ni(II)‐Incorporated Covalent Organic Framework for Metallaphotoredox Catalysis

• Published in: Chemistry : a European journal Vol. 30; no. 10; pp. e202303476 - n/a
• Main Authors: Hu, Hai‐Chao, Wang, Zhi‐Peng, Liang, Lin, Du, Xin‐Yu, Li, Ting, Feng, Jie, Xiao, Tian‐Tian, Jin, Ze‐Ming, Ding, San‐Yuan, Liu, Qiang, Lu, Liang‐Qiu, Xiao, Wen‐Jing, Wang, Wei
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 16.02.2024; Wiley Subscription Services, Inc
• Subjects: Active sites; bottom-up strategy; Catalysis; Catalysts; Catalytic activity; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; covalent organic framework; Cross coupling; cross-coupling reactions; metallaphotoredox catalysis; Nickel; Physical Sciences; Recyclability; Science & Technology; Transition metals; bottom-up strategy; NICKEL CATALYSIS; PHOTOREDOX; TRANSITION-METAL; metallaphotoredox catalysis; ARYL; CRYSTALLINE; EFFICIENT; covalent organic framework; cross-coupling reactions; PHOTOCATALYST; TRANSFORMATIONS
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202303476

The construction of an all‐in‐one catalyst, in which the photosensitizer and the transition metal site are close to each other, is important for improving the efficiency of metallaphotoredox catalysis. However, the development of convenient synthetic strategies for the precise construction of an all‐in‐one catalyst remains a challenging task due to the requirement of precise installation of the catalytic sites. Herein, we have successfully established a facile bottom‐up strategy for the direct synthesis of Ni(II)‐incorporated covalent organic framework (COF), named LZU‐713@Ni, as a versatile all‐in‐one metallaphotoredox catalyst. LZU‐713@Ni showed excellent activity and recyclability in the photoredox/nickel‐catalyzed C−O, C−S, and C−P cross‐coupling reactions. Notably, this catalyst displayed a better catalytic activity than its homogeneous analogues, physically mixed dual catalyst system, and, especially, LZU‐713/Ni which was prepared through post‐synthetic modification. The improved catalytic efficiency of LZU‐713@Ni should be attributed to the implementation of bottom‐up strategy, which incorporated the fixed, ordered, and abundant catalytic sites into its framework. This work sheds new light on the exploration of concise and effective strategies for the construction of multifunctional COF‐based photocatalysts. We developed a facile bottom‐up strategy to synthesize Ni(II)‐incorporated covalent organic framework (LZU‐713@Ni) as heterogeneous all‐in‐one metallaphotoredox catalyst. LZU‐713@Ni showed excellent activity and recyclability in photoredox/nickel‐catalyzed C−O, C−S, and C−P cross‐coupling reactions. The superiority of bottom‐up strategy was exemplified by the increased activity of LZU‐713@Ni compared to both the dual catalyst system and LZU‐713/Ni prepared via post‐synthetic modification.