Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Synthesis of covalent organic frameworks via coupling polymerization

Nature Synthesis volume 5, pages 199–208 (2026) Cite this article

Subjects

Abstract

Covalent organic frameworks (COFs) are crystalline porous polymers traditionally assembled via reversible condensation polymerizations to form ordered structures. In contrast, coupling reactions have historically led to amorphous, disordered materials due to their irreversible nature, posing a challenge for COF synthesis. Here we present a microinterfacial solvothermal polymerization strategy that overcomes this limitation by harnessing irreversible coupling reactions to construct crystalline porous framework materials. By spatially confining monomers and intermediates at organic–water interfaces, our approach drives Glaser–Eglinton coupling polymerization of ethynyl-functionalized monomers to form two-dimensional sp-carbon-conjugated COFs with discrete hexagonal, tetragonal and kagome topologies. The resulting frameworks allow extended in-plane π conjugation and out-of-plane electronic coupling and exhibit an eight-order-of-magnitude enhancement in electrical conductivity upon chemical oxidation with iodine in pores. These materials confine free radicals at nodal sites, where their spins are aligned in different ways to develop paramagnetic, antiferromagnetic and ferromagnetic phases, evolving semiconducting magnets with distinct spin coherence controlled by the COF topology. These findings showcase the use of coupling reactions in COF synthesis to synthesize an interesting class of organic semiconducting magnets.

The alternative text for this image may have been generated using AI.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Synthesis of COFs.
The alternative text for this image may have been generated using AI.
Fig. 2: Structure.
The alternative text for this image may have been generated using AI.
Fig. 3: Radical behaviour and spin–spin interactions.
The alternative text for this image may have been generated using AI.
Fig. 4: Magnetization and spin alignment.
The alternative text for this image may have been generated using AI.

Similar content being viewed by others

Data availability

The experimental and theoretical data that support the findings of this study are provided as source data: Supplementary Dataset 1 for the cif file of spC4-COF-1; Supplementary Dataset 2 for the cif file of spC4-COF-2; Supplementary Dataset 3 for the cif file of spC4-COF-3.

References

  1. Cote, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).

    Article  CAS  PubMed  Google Scholar 

  2. Côté, A. P., El-Kaderi, H. M., Furukawa, H., Hunt, J. R. & Yaghi, O. M. Reticular synthesis of microporous and mesoporous 2D covalent organic frameworks. J. Am. Chem. Soc. 129, 12914–12915 (2007).

    Article  PubMed  Google Scholar 

  3. Mu, X. et al. Ketazine-linked crystalline porous covalent organic frameworks. J. Am. Chem. Soc. 146, 25118–25124 (2024).

    Article  CAS  PubMed  Google Scholar 

  4. Jin, E. et al. Two-dimensional sp2 carbon–conjugated covalent organic frameworks. Science 357, 673–676 (2017).

    Article  CAS  PubMed  Google Scholar 

  5. Rupainwar, R., Pandey, J., Smriti, S. & Ruchi, R. The importance and applications of Knoevenagel reaction. Orient. J. Chem. 35, 423–429 (2019).

    Article  CAS  Google Scholar 

  6. Mandal, S. et al. Review of the aldol reaction. Synth. Commun. 46, 1327–1342 (2016).

    Article  CAS  Google Scholar 

  7. Wan, S., Guo, J., Kim, J. & Jiang, D. A belt-shaped, blue luminescent and semiconducting covalent organic framework. Angew. Chem. Int. Ed. 47, 8826–8830 (2008).

    Article  CAS  Google Scholar 

  8. Feng, X. et al. An ambipolar conducting covalent organic framework with self-sorted and periodic electron donor–acceptor ordering. Adv. Mater. 24, 3026–3031 (2012).

    Article  CAS  PubMed  Google Scholar 

  9. Jin, S. et al. Creation of superheterojunction polymers via direct polycondensation: segregated and bicontinuous donor–acceptor π-columnar arrays in covalent organic frameworks for long-lived charge separation. J. Am. Chem. Soc. 137, 7817–7828 (2015).

    Article  CAS  PubMed  Google Scholar 

  10. Xu, H., Gao, J. & Jiang, D. Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts. Nat. Chem. 7, 905–912 (2015).

    Article  CAS  PubMed  Google Scholar 

  11. Ma, S. T. et al. Photocatalytic hydrogen production on a sp2-carbon-linked covalent organic framework. Angew. Chem. Int. Ed. 61, e202208919 (2022).

    Article  CAS  Google Scholar 

  12. He, T. et al. Integrated interfacial design of covalent organic framework photocatalysts to promote hydrogen evolution from water. Nat. Commun. 14, 329 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Liu, R. et al. Linkage-engineered donor–acceptor covalent organic frameworks for optimal photosynthesis of hydrogen peroxide from water and air. Nat. Catal. 7, 195–206 (2024).

    Article  Google Scholar 

  14. Zhao, X., Pachfule, P. & Thomas, A. Covalent organic frameworks (COFs) for electrochemical applications. Chem. Soc. Rev. 50, 6871–6913 (2021).

    Article  CAS  PubMed  Google Scholar 

  15. Tan, K. T. et al. Covalent organic frameworks. Nat. Rev. Methods Primers 3, 1 (2023).

    Article  CAS  Google Scholar 

  16. Haase, F. & Lotsch, B. V. Solving the COF trilemma: towards crystalline, stable and functional covalent organic frameworks. Chem. Soc. Rev. 49, 8469–8500 (2020).

    Article  CAS  PubMed  Google Scholar 

  17. Geng, K. et al. Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120, 8814–8933 (2020).

    Article  CAS  PubMed  Google Scholar 

  18. Segura, J. L., Mancheño, M. J. & Zamora, F. Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications. Chem. Soc. Rev. 45, 5635–5671 (2016).

    Article  CAS  PubMed  Google Scholar 

  19. Feng, X., Ding, X. & Jiang, D. Covalent organic frameworks. Chem. Soc. Rev. 41, 6010–6022 (2012).

    Article  CAS  PubMed  Google Scholar 

  20. Evans, A. M. et al. Two-dimensional polymers and polymerizations. Chem. Rev. 122, 442–564 (2022).

    Article  CAS  PubMed  Google Scholar 

  21. Haug, W. K., Moscarello, E. M., Wolfson, E. R. & McGrier, P. L. The luminescent and photophysical properties of covalent organic frameworks. Chem. Soc. Rev. 49, 839–864 (2020).

    Article  CAS  PubMed  Google Scholar 

  22. Li, Y., Chen, W., Xing, G., Jiang, D. & Chen, L. New synthetic strategies toward covalent organic frameworks. Chem. Soc. Rev. 49, 2852–2868 (2020).

    Article  CAS  PubMed  Google Scholar 

  23. Zhou, Z. et al. Carbon dioxide capture from open air using covalent organic frameworks. Nature 635, 96–101 (2024).

    Article  CAS  PubMed  Google Scholar 

  24. Zhang, W. et al. Reconstructed covalent organic frameworks. Nature 604, 72–79 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Xu, Y., Jin, S., Xu, H., Nagai, A. & Jiang, D. Conjugated microporous polymers: design, synthesis and application. Chem. Soc. Rev. 42, 8012–8031 (2013).

    Article  CAS  PubMed  Google Scholar 

  26. Voit, B. I. & Lederer, A. Hyperbranched and highly branched polymer architectures—synthetic strategies and major characterization aspects. Chem. Rev. 109, 5924–5973 (2009).

    Article  CAS  PubMed  Google Scholar 

  27. Taylor, D., Dalgarno, S. J., Xu, Z. & Vilela, F. Conjugated porous polymers: incredibly versatile materials with far-reaching applications. Chem. Soc. Rev. 49, 3981–4042 (2020).

    Article  CAS  PubMed  Google Scholar 

  28. Wu, S. et al. Toward two-dimensional π-conjugated covalent organic radical frameworks. Angew. Chem. Int. Ed. 57, 8007–8011 (2018).

    Article  CAS  Google Scholar 

  29. Zhou, D., Tan, X., Wu, H., Tian, L. & Li, M. Synthesis of C-C bonded two-dimensional conjugated covalent organic framework films by Suzuki polymerization on a liquid-liquid interface. Angew. Chem. Int. Ed. 58, 1376–1381 (2019).

    Article  CAS  Google Scholar 

  30. Kang, F. et al. On-surface synthesis of hydrogen-substituted γ-graphdiyne with high efficiency. CCS Chem. 6, 2644–2651 (2024).

    Article  CAS  Google Scholar 

  31. Zhang, Y. Q. et al. Homo-coupling of terminal alkynes on a noble metal surface. Nat. Commun. 3, 1286 (2012).

    Article  PubMed  Google Scholar 

  32. Liu, H. et al. Interfacial synthesis of conjugated crystalline 2D fluorescent polymer film containing aggregation-induced emission unit. Small 15, 1804519 (2019).

    Article  Google Scholar 

  33. Matsuoka, R. et al. Expansion of the graphdiyne family: a triphenylene-cored analogue. ACS Appl. Mater. Interfaces 11, 2730–2733 (2019).

    Article  CAS  PubMed  Google Scholar 

  34. Xu, T. et al. Topology modulation of tetraphenylethylene graphdiyne at a liquid–liquid interface. Nano Res. 17, 4661–4667 (2024).

    Article  CAS  Google Scholar 

  35. Liu, Y., Fan, Z., Sun, Y., Guo, X. & Jin, Z. Mechanochemical synthesis of pyrenyl graphdiyne coupling CdS/CeO2, constructing a ternary photocatalyst toward efficient hydrogen evolution. ACS Appl. Energy Mater. 6, 9743–9755 (2023).

    Article  CAS  Google Scholar 

  36. Heimann, R. B., Evsvukov, S. E. & Koga, Y. Carbon allotropes: a suggested classification scheme based on valence orbital hybridization. Carbon 35, 1654–1658 (1997).

    Article  CAS  Google Scholar 

  37. Li, G., Li, Y., Lui, H., Guo, Y. & Li, Y. et al. Architecture of graphdiyne nanoscale films. Chem. Commun. 46, 3256–3258 (2010).

    Article  CAS  Google Scholar 

  38. Miller, J. Ferromagnetic molecular charge-transfer complexes. Chem. Rev. 88, 201–220 (1988).

    Article  CAS  Google Scholar 

  39. Siemsen, P., Livingston, R. C. & Diederich, F. Acetylenic coupling: a powerful tool in molecular construction. Angew. Chem. Int. Ed. 39, 2632–2657 (2000).

    Article  CAS  Google Scholar 

  40. Sindhu, K. S. & Anilkumar, G. Recent advances and applications of Glaser coupling employing greener protocols. RSC Adv. 4, 27867–27887 (2014).

    Article  CAS  Google Scholar 

  41. Jin, E. et al. Topology-templated synthesis of crystalline porous covalent organic frameworks. Angew. Chem. Int. Ed. 59, 12162–12169 (2020).

    Article  CAS  Google Scholar 

  42. Matsuoka, R. et al. Crystalline graphdiyne nanosheets produced at a gas/liquid or liquid/liquid interface. J. Am. Chem. Soc. 139, 3145–3152 (2017).

    Article  CAS  PubMed  Google Scholar 

  43. Schwarz, D. et al. Tuning the porosity and photocatalytic performance of triazine‐based graphdiyne polymers through polymorphism. ChemSusChem 12, 194–199 (2019).

    Article  CAS  PubMed  Google Scholar 

  44. Song, Y., Fan, J. B. & Wang, S. Recent progress in interfacial polymerization. Mater. Chem. Front. 1, 1028–1040 (2017).

    Article  CAS  Google Scholar 

  45. Matsumoto, M. et al. Lewis-acid-catalyzed interfacial polymerization of covalent organic framework films. Chem 4, 308–317 (2018).

    Article  CAS  Google Scholar 

  46. Thomas, S. et al. Electronic structure of two-dimensional π‑conjugated covalent organic frameworks. Chem. Mater. 31, 3051–3065 (2019).

    Article  CAS  Google Scholar 

  47. Xie, Y. et al. Efficient and simultaneous capture of iodine and methyl iodide achieved by a covalent organic framework. Nat. Commun. 13, 2878 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  48. Oanta, A. K. et al. Electronic spin qubit candidates arrayed within layered two-dimensional polymers. J. Am. Chem. Soc. 145, 689–696 (2023).

    Article  CAS  PubMed  Google Scholar 

  49. Chen, Q., Adeniran, O., Liu, Z.-F., Zhang, Z. & Awaga, K. Graphite-like charge storage mechanism in a 2D π–d conjugated metal–organic framework revealed by stepwise magnetic monitoring. J. Am. Chem. Soc. 145, 1062–1071 (2023).

    Article  CAS  PubMed  Google Scholar 

  50. Mori, T. et al. Metal–insulator transition in the organic metal (TTM−TTP)I3 with a one-dimensional half-filled band. Phys. Rev. Lett. 79, 1702–1705 (1997).

    Article  CAS  Google Scholar 

  51. Ning, S. et al. A 2D antiferromagnetic coordination polymer constructed by benzotriazole-5-carboxylic acid. Inorg. Chem. Commun. 153, 110789 (2023).

    Article  CAS  Google Scholar 

  52. Bronstein, H., Nielsen, C. B., Schroeder, B. C. & McCulloch, I. The role of chemical design in the performance of organic semiconductors. Nat. Rev. Chem. 4, 66–77 (2020).

    Article  CAS  PubMed  Google Scholar 

  53. Henson, Z., Müllen, K. & Bazan, G. Design strategies for organic semiconductors beyond the molecular formula. Nat. Chem. 4, 699–704 (2012).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the funding from Singapore MOE Tier 2 grant (T2EP10221-0012) and Singapore NRF A*STAR grant (U2102d2004). We thank J. Li for TEM measurements and H. Zheng for the conductivity tests.

Author information

Authors and Affiliations

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

    Zhuoer Li, Shanshan Tao & Donglin Jiang

  2. School of Science and Technology, Nottingham Trent University, Nottingham, UK

    Matthew Addicoat

  3. Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki, Japan

    Toshikazu Nakamura

Authors
  1. Zhuoer Li
    View author publications

    Search author on:PubMed Google Scholar

  2. Shanshan Tao
    View author publications

    Search author on:PubMed Google Scholar

  3. Matthew Addicoat
    View author publications

    Search author on:PubMed Google Scholar

  4. Toshikazu Nakamura
    View author publications

    Search author on:PubMed Google Scholar

  5. Donglin Jiang
    View author publications

    Search author on:PubMed Google Scholar

Contributions

D.J. conceived and led the project, acquired funding and administrated the project. Z.L. conducted the experiments and developed the synthetic methodology. S.T. performed experiments. M.A. conducted structural simulations. T.N. conducted temperature-dependent EPR measurements. The paper was drafted by Z.L., and rewritten and edited by D.J. All authors discussed the results and contributed to the paper.

Corresponding author

Correspondence to Donglin Jiang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Jianzhuang Jiang, Zhenjie Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Characterization of chemical structure.

a, FT IR spectra of TEPB (black curve) and spC4-COF-1 (red curve). b, FT IR spectra of TEPPy monomer (black curve), spC4-COF-2 (red curve) and spC4-COF-3 (blue curve). c, 13C solid-state CP/MAS NMR spectrum and peak assignments of spC4-COF-1. d, Solid-state 13C CP/MAS NMR spectrum of spC4-COF-2 and peak assignments. e, Solid-state 13C CP/MAS NMR spectrum and peak assignments of spC4-COF-3. In c–d, * show side peaks.

Source Data

Extended Data Fig. 2 Porosity of COFs.

a, Nitrogen absorption and desorption isotherm curves of spC4-COF-1. b, Pore size distribution and pore volume of spC4-COF-1. c, Nitrogen absorption and desorption isotherm curves of spC4-COF-2. d, Pore size distribution and pore volume for spC4-COF-2. e, Nitrogen absorption and desorption isotherm curves of spC4-COF-3. f, Pore size distribution and pore volume for spC4-COF-3. In a, c, e, filled circles for absorption isotherm and open circles for desorption isotherm; in b, d and f, filled circles for pore volume and open circles for pore size distribution.

Source Data

Extended Data Fig. 3 I–V curves of iodine-oxidized COFs.

a–c, I–V curves of the pristine spC4-COFs (black curve) and iodine-doped I2@spC-COFs (red curve) of I2@spC4-COF-1 (a), I2@spC4-COF-2 (b) and I2@spC4-COF-3 (c).

Source Data

Extended Data Fig. 4 M–H curves of iodine-oxidized COFs.

a–c, Magnetic (M)–applied field (H) profiles of I2@spC4-COF-1 (a), I2@spC4-COF-2 (b) and I2@spC4-COF-3 (c), at different temperatures (red, 2 K; violet, 5 K; purple, 10 K; blue, 20 K; green, 50 K; cyan, 100 K; orange, 200 K; brown, 300 K).

Source Data

Supplementary information

Supplementary Information (download PDF )

Materials and methods, Synthetic procedures, Supplementary Tables 1–5, Figs. 1–14, captions for Supplementary Datasets 1–3 and references.

Supplementary Data 1

Cif file for spC4-COF-1.

Supplementary Data 2

Cif file for spC4-COF-2.

Supplementary Data 3

Cif file for spC4-COF-3.

Supplementary Video 1 (download MOV )

Video for spC4-COF-1.

Supplementary Video 2 (download MOV )

Video spC4-COF-2.

Supplementary Video 3 (download MOV )

Video for spC4-COF-3.

Supplementary Data 4 (download XLSX )

Statistical source data for the figures in the supplementary information.

Source data

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, Z., Tao, S., Addicoat, M. et al. Synthesis of covalent organic frameworks via coupling polymerization. Nat. Synth 5, 199–208 (2026). https://doi.org/10.1038/s44160-025-00895-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s44160-025-00895-4

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing