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Topochemical conversion of an imine- into a thiazole-linked covalent organic framework enabling real structure analysis

Author

Listed:
  • Frederik Haase

    (Max Planck Institute for Solid State Research
    Department of Chemistry, Ludwig-Maximilians-Universität München)

  • Erik Troschke

    (Department of Inorganic Chemistry 1, TU Dresden)

  • Gökcen Savasci

    (Max Planck Institute for Solid State Research
    Department of Chemistry, Ludwig-Maximilians-Universität München)

  • Tanmay Banerjee

    (Max Planck Institute for Solid State Research)

  • Viola Duppel

    (Max Planck Institute for Solid State Research)

  • Susanne Dörfler

    (Fraunhofer Institute for Material and Beam Technology (IWS))

  • Martin M. J. Grundei

    (Department of Chemistry, Ludwig-Maximilians-Universität München)

  • Asbjörn M. Burow

    (Department of Chemistry, Ludwig-Maximilians-Universität München)

  • Christian Ochsenfeld

    (Department of Chemistry, Ludwig-Maximilians-Universität München)

  • Stefan Kaskel

    (Department of Inorganic Chemistry 1, TU Dresden
    Fraunhofer Institute for Material and Beam Technology (IWS))

  • Bettina V. Lotsch

    (Max Planck Institute for Solid State Research
    Department of Chemistry, Ludwig-Maximilians-Universität München)

Abstract

Stabilization of covalent organic frameworks (COFs) by post-synthetic locking strategies is a powerful tool to push the limits of COF utilization, which are imposed by the reversible COF linkage. Here we introduce a sulfur-assisted chemical conversion of a two-dimensional imine-linked COF into a thiazole-linked COF, with full retention of crystallinity and porosity. This post-synthetic modification entails significantly enhanced chemical and electron beam stability, enabling investigation of the real framework structure at a high level of detail. An in-depth study by electron diffraction and transmission electron microscopy reveals a myriad of previously unknown or unverified structural features such as grain boundaries and edge dislocations, which are likely generic to the in-plane structure of 2D COFs. The visualization of such real structural features is key to understand, design and control structure–property relationships in COFs, which can have major implications for adsorption, catalytic, and transport properties of such crystalline porous polymers.

Suggested Citation

  • Frederik Haase & Erik Troschke & Gökcen Savasci & Tanmay Banerjee & Viola Duppel & Susanne Dörfler & Martin M. J. Grundei & Asbjörn M. Burow & Christian Ochsenfeld & Stefan Kaskel & Bettina V. Lotsch, 2018. "Topochemical conversion of an imine- into a thiazole-linked covalent organic framework enabling real structure analysis," Nature Communications, Nature, vol. 9(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-04979-y
    DOI: 10.1038/s41467-018-04979-y
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    Cited by:

    1. Baokun Liang & Yingying Zhang & Christopher Leist & Zhaowei Ou & Miroslav Položij & Zhiyong Wang & David Mücke & Renhao Dong & Zhikun Zheng & Thomas Heine & Xinliang Feng & Ute Kaiser & Haoyuan Qi, 2022. "Optimal acceleration voltage for near-atomic resolution imaging of layer-stacked 2D polymer thin films," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Yongliang Yang & Ling Yu & Tiancheng Chu & Hongyun Niu & Jun Wang & Yaqi Cai, 2022. "Constructing chemical stable 4-carboxyl-quinoline linked covalent organic frameworks via Doebner reaction for nanofiltration," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. Maria-Anna Gatou & Panagiota Bika & Thomas Stergiopoulos & Panagiotis Dallas & Evangelia A. Pavlatou, 2021. "Recent Advances in Covalent Organic Frameworks for Heavy Metal Removal Applications," Energies, MDPI, vol. 14(11), pages 1-26, May.
    4. Jia-Rui Wang & Kepeng Song & Tian-Xiang Luan & Ke Cheng & Qiurong Wang & Yue Wang & William W. Yu & Pei-Zhou Li & Yanli Zhao, 2024. "Robust links in photoactive covalent organic frameworks enable effective photocatalytic reactions under harsh conditions," Nature Communications, Nature, vol. 15(1), pages 1-17, December.

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