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Steric effect of intermediates induces formation of three-dimensional covalent organic frameworks

Author

Listed:
  • Jiawei Lai

    (Beijing Normal University)

  • Shikai Liu

    (Beijing Normal University)

  • Wenjie Ma

    (Chinese Academy of Sciences (CAS)
    University of Chinese Academy of Sciences)

  • Fei Wu

    (Beijing Normal University)

  • Ping Yu

    (Chinese Academy of Sciences (CAS)
    University of Chinese Academy of Sciences)

  • Lanqun Mao

    (Beijing Normal University)

Abstract

Constructing three-dimensional covalent organic frameworks (3D COFs) remains a significant challenge compared to other areas of reticular chemistry. Most existing methods for constructing 3D COFs emphasize the necessity of at least one precursor being extended into 3D space. As a result, designing and synthesizing precursors with specific stereoconformations has become a dominant strategy for discovering new 3D COFs. In this study, we leverage the principle that the steric hindrance of intermediates during COF formation is inherently greater than that of the precursors. We demonstrate a strategy utilizing multinode porphyrin blocks with eight rotatable knots to create intermediates with steric hindrance-confined rigid stereoconformations, which can be viewed as active precursors for guiding 3D formation of COFs with high crystallinity. This approach paves an avenue to self-adaptive COF growth towards diverse 3D topologies that may circumvent obstacles for traditional precursor synthesis.

Suggested Citation

  • Jiawei Lai & Shikai Liu & Wenjie Ma & Fei Wu & Ping Yu & Lanqun Mao, 2025. "Steric effect of intermediates induces formation of three-dimensional covalent organic frameworks," Nature Communications, Nature, vol. 16(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-61373-1
    DOI: 10.1038/s41467-025-61373-1
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    References listed on IDEAS

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    1. Dongyang Zhu & Yifan Zhu & Yu Chen & Qianqian Yan & Han Wu & Chun-Yen Liu & Xu Wang & Lawrence B. Alemany & Guanhui Gao & Thomas P. Senftle & Yongwu Peng & Xiaowei Wu & Rafael Verduzco, 2023. "Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    2. Youshi Lan & Xianghao Han & Minman Tong & Hongliang Huang & Qingyuan Yang & Dahuan Liu & Xin Zhao & Chongli Zhong, 2018. "Materials genomics methods for high-throughput construction of COFs and targeted synthesis," Nature Communications, Nature, vol. 9(1), pages 1-10, December.
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