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Covalent organic frameworks

Nature Reviews Methods Primers volume 3, Article number: 1 (2023) Cite this article

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Abstract

The dream to prepare well-defined materials drives the methodological evolution for molecular synthesis, structural control and materials manufacturing. Among various methods, chemical approaches to design, synthesize, control and engineer small molecules, polymers and networks offer the fundamental strategies. Merging covalent bonds and non-covalent interactions into one method to establish a complex structural composition for specific functions, mimicking biological systems such as DNA, RNA and proteins, is at the centre of chemistry and materials science. Covalent organic frameworks (COFs) are a class of crystalline porous polymers that enable the integration of organic units into highly ordered structures via polymerization. This polymerization system is unique as it deploys covalent bonds to construct the primary order structures of polymeric backbones via polycondensation and leverages on non-covalent interactions to create the high order structures of polymeric networks via supramolecular polymerization in a one-pot reaction system. This Primer covers all aspects of the field of COFs from chemistry to physics, materials and applications, and outlines the design principle, experimental methods, characterization and applications, with an aim to show a concise yet full picture of the field. The key fundamental issues to be addressed are analysed with an outlook on the future major directions from different perspectives.

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Fig. 1: Structural construction of COFs.
Fig. 2: Topology diagram principle in guiding the design of COFs.
Fig. 3: Reactions for linkage formation.
Fig. 4: Principle for aniline-aided growth of single-crystal 3D COFs.
Fig. 5: Characterization results.
Fig. 6: Structural observation results.
Fig. 7: Applications of COFs.

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Acknowledgements

D.J. acknowledges Singapore Ministry of Education (MOE) Tier 2 grants (MOE-T2EP10220-0004 and MOE-T2EP10221-0006), MOE Tier 1 grants (A-0008368-00-00 and A-0008369-00-00) and an A* star grant (U2102d2004). A.T. is grateful for support from the Deutsche Forschungsgemeinschaft (DFG; German Research Foundation) under Germany′s Excellence Strategy — EXC 2008-390540038 — UniSysCat. S.G. acknowledges the Alexander von Humboldt Stiftung for a postdoctoral fellowship. Z.W. and X.F. acknowledge the EU Graphene Flagship (GrapheneCore3, no. 881603), ERC Consolidator Grant (T2DCP), DFG project (2D polyanilines, no. 426572620), CRC 1415 (Chemistry of Synthetic Two-Dimensional Materials, no. 417590517) and SPP 2244 (2DMP). F.Z. and D.R.-S.-M. acknowledge Ministerio de Ciencia e Innovación through project PID2019-106268GB-C32. W.W. acknowledges financial support by the National Natural Science Foundation of China (Nos. 92056202 and 21903041) and the 111 project 2.0 (BP1221004). N.H. acknowledges the National Natural Science Foundation of China (No. 92163131).

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Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Ke Tian Tan & Donglin Jiang

  2. Inorganic and Physical Chemistry Laboratory, CSIR — Central Leather Research Institute, Chennai, India

    Samrat Ghosh

  3. Department of Chemistry/Functional Materials, Technische Universität Berlin, Berlin, Germany

    Samrat Ghosh & Arne Thomas

  4. Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Zhiyong Wang & Xinliang Feng

  5. Department of Synthetic Materials and Functional Devices, Max Planck Institute for Microstructure Physics, Halle, Germany

    Zhiyong Wang & Xinliang Feng

  6. MOE Key Laboratory of Macromolecular Synthesis and Functionalisation, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, China

    Fuxiang Wen & Ning Huang

  7. Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, Spain

    David Rodríguez-San-Miguel & Felix Zamora

  8. College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China

    Jie Feng & Wei Wang

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  1. Ke Tian Tan
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Contributions

All authors researched data for the article. All authors contributed substantially to discussion of the content. S.G. and A.T. wrote Irreversible reactions. Z.W. and X.F. wrote Thin films, Composites and Outlook. F.W. and N.H. wrote Reproducibility and data deposition, Limitations and optimizations, and Outlook. D.R.-S.-M. and F.Z. wrote Processable COFs and Energy storage. J.F. and W.W. wrote Single-crystal formation. D.J. and K.T.T. wrote the rest of the sections, reviewed and edited the manuscript and prepared the figures before submission.

Corresponding author

Correspondence to Donglin Jiang.

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Nature Reviews Methods Primers thanks Kailong Jin, Fan Zhang, Zhongyi Jiang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Glossary

π interactions

Non-covalent interactions that involve the π system.

Covalent bonds

Regions of relatively high electron density between nuclei that arise at least partly from sharing of electrons and give rise to an attractive force and characteristic internuclear distance.

Knots

Organic molecules with multiple reactive points to enable the branching of a polymeric backbone and that locate on the lattice vertex.

Linkers

Organic molecules with multiple reactive points that connect knots.

Non-covalent interactions

Forces that do not involve the sharing of electrons but involve dispersed electromagnetic interactions.

Polycondensation reactions

Polymerizations in which the growth of polymer chains proceeds by condensation reactions between molecules of all degrees of polymerization.

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Tan, K.T., Ghosh, S., Wang, Z. et al. Covalent organic frameworks. Nat Rev Methods Primers 3, 1 (2023). https://doi.org/10.1038/s43586-022-00181-z

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