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:

Partitioning the interlayer space of covalent organic frameworks by embedding pseudorotaxanes in their backbones

Nature Chemistry volume 12, pages 1115–1122 (2020)Cite this article

Subjects

Abstract

Mono- or few-layer sheets of covalent organic frameworks (COFs) represent an attractive platform of two-dimensional materials that hold promise for tailor-made functionality and pores, through judicious design of the COF building blocks. But although a wide variety of layered COFs have been synthesized, cleaving their interlayer stacking to obtain COF sheets of uniform thickness has remained challenging. Here, we have partitioned the interlayer space in COFs by incorporating pseudorotaxane units into their backbones. Macrocyclic hosts based on crown ethers were embedded into either a ditopic or a tetratopic acylhydrazide building block. Reaction with a tritopic aldehyde linker led to the formation of acylhydrazone-based layered COFs in which one basal plane is composed of either one layer, in the case of the ditopic macrocyclic component, or two adjacent layers covalently held together by its tetratopic counterpart. When a viologen threading unit is introduced, the formation of a host–guest complex facilitates the self-exfoliation of the COFs into crystalline monolayers or bilayers, respectively.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: A general strategy for design and construction of self-exfoliated COFs with well-defined layer numbers of covalent linkages.
Fig. 2: Synthesis of macrocycle- and pseudorotaxane-based COFs.
Fig. 3: Characterization of the crystallinity of MCOF-1 and the pseudorotaxane complexation in RCOF-1.
Fig. 4: Exfoliation of RCOF-1 and characterization of its crystallinity.
Fig. 5: AFM study of RCOF-0 and RCOF-1.

Similar content being viewed by others

Data availability

X-ray crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/) with CCDC reference numbers 1863696 (single-crystal Cy1-MVPF6), and 2006788 (single-crystal CyHz0-MVPF6). A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the paper and its Supplementary Information. Data are also available from the corresponding author upon reasonable request.

References

  1. Colson,, J. W. & Dichtel,, W. R. Rationally synthesized two-dimensional polymers. Nat. Chem. 5, 453–465 (2013).

    Article  CAS  Google Scholar 

  2. Ding, S.-Y. & Wang, W. Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 42, 548–568 (2013).

    Article  CAS  Google Scholar 

  3. Huang, N., Wang, P. & Jiang, D. Covalent organic frameworks: a materials platform for structural and functional designs. Nat. Rev. Mater. 1, 16068 (2016).

    Article  CAS  Google Scholar 

  4. Segura, J. L., Mancheno, 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  Google Scholar 

  5. Diercks, C. S. & Yaghi, O. M. The atom, the molecule, and the covalent organic framework. Science 355, eaal1585 (2017).

    Article  Google Scholar 

  6. Li,, X., Yadav,, P. & Loh,, K. P. Function-oriented synthesis of two-dimensional (2D) covalent organic frameworks – from 3D solids to 2D sheets. Chem. Soc. Rev. 49, 4835–4866 (2020).

    Article  CAS  Google Scholar 

  7. Xu, H.-S. et al. Single crystal of a one-dimensional metallo-covalent organic framework. Nat. Commun. 11, 1434 (2020).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  9. El-Kaderi, H. M. et al. Designed synthesis of 3D covalent organic frameworks. Science 316, 268–272 (2007).

    Article  CAS  Google Scholar 

  10. Lyle, S. J., Waller, P. J. & Yaghi, O. M. Covalent organic frameworks: organic chemistry extended into two and three dimensions. Trends Chem. 1, 172–184 (2019).

    Article  CAS  Google Scholar 

  11. Berlanga, I. et al. Delamination of layered covalent organic frameworks. Small 7, 1207–1211 (2011).

    Article  CAS  Google Scholar 

  12. Bunck, D. N. & Dichtel, W. R. Bulk synthesis of exfoliated two-dimensional polymers using hydrazone-linked covalent organic frameworks. J. Am. Chem. Soc. 135, 14952–14955 (2013).

    Article  CAS  Google Scholar 

  13. Chandra, S. et al. Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination. J. Am. Chem. Soc. 135, 17853–17861 (2013).

    Article  CAS  Google Scholar 

  14. Peng, Y. et al. Ultrathin two-dimensional covalent organic framework nanosheets: preparation and application in highly sensitive and selective DNA detection. J. Am. Chem. Soc. 139, 8698–8704 (2017).

    Article  CAS  Google Scholar 

  15. Khayum, M. A. et al. Chemically delaminated free-standing ultrathin covalent organic nanosheets. Angew. Chem. Int. Ed. 55, 15604–15608 (2016).

    Article  CAS  Google Scholar 

  16. Colson, J. W. et al. Oriented 2D covalent organic framework thin films on single-layer graphene. Science 332, 228–231 (2011).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. Hao, Q. et al. Confined synthesis of two-dimensional covalent organic framework thin films within superspreading water layer. J. Am. Chem. Soc. 140, 12152–12158 (2018).

    Article  CAS  Google Scholar 

  19. Zhou, T.-Y., Lin, F., Li, Z.-T. & Zhao, X. Single-step solution-phase synthesis of free-standing two-dimensional polymers and their evolution into hollow spheres. Macromolecules 46, 7745–7752 (2013).

    Article  CAS  Google Scholar 

  20. Dienstmaier, J. F. et al. Synthesis of well-ordered COF monolayers: surface growth of nanocrystalline precursors versus direct on-surface polycondensation. ACS Nano 5, 9737–9745 (2011).

    Article  CAS  Google Scholar 

  21. Xu, L. et al. Surface-confined single-layer covalent organic framework on single-layer graphene grown on copper foil. Angew. Chem. Int. Ed. 53, 9564–9568 (2014).

    Article  CAS  Google Scholar 

  22. Chen, C. et al. Local electronic structure of a single-layer porphyrin-containing covalent organic framework. ACS Nano 12, 385–391 (2018).

    Article  CAS  Google Scholar 

  23. Joshi, T. et al. Local electronic structure of molecular heterojunctions in a single-layer 2D covalent organic framework. Adv. Mater. 0, 1805941 (2018).

    Google Scholar 

  24. Lindoy L. F. The Chemistry of Macrocyclic Ligand Complexes (Cambridge Univ. Press, 1989).

  25. Stoddart, J. F. The chemistry of the mechanical bond. Chem. Soc. Rev. 38, 1802–1820 (2009).

    Article  CAS  Google Scholar 

  26. Rambo, B. M., Gong, H.-Y., Oh, M. & Sessler, J. L. The “Texas-Sized” Molecular Box: A versatile building block for the construction of anion-directed mechanically interlocked structures. Acc. Chem. Res. 45, 1390–1401 (2012).

    Article  CAS  Google Scholar 

  27. Stoddart, J. F. Mechanically interlocked molecules (MIMs)—molecular shuttles, switches, and machines (Nobel Lecture). Angew. Chem., Int. Ed. 56, 11094–11125 (2017).

    Article  CAS  Google Scholar 

  28. Li, Q. et al. Docking in metal–organic frameworks. Science 325, 855 (2009).

    Article  CAS  Google Scholar 

  29. Vukotic, V. N., Harris, K. J., Zhu, K., Schurko, R. W. & Loeb, S. J. Metal–organic frameworks with dynamic interlocked components. Nat. Chem. 4, 456–460 (2012).

    Article  CAS  Google Scholar 

  30. Li, X. et al. Rapid, scalable construction of highly crystalline acylhydrazone two-dimensional covalent organic frameworks via dipole-induced antiparallel stacking. J. Am. Chem. Soc. 142, 4932–4943 (2020).

    Article  CAS  Google Scholar 

  31. Allwood B. L., Spencer N., Shahriari-Zavareh H., Stoddart J. F. & Williams D. J. Complexation of Paraquat by a bisparaphenylene-34-crown-10 derivative. J. Chem. Soc. Chem. Commun. 1064–1066 (1987).

  32. Li, X. et al. Tuneable near white-emissive two-dimensional covalent organic frameworks. Nat. Commun. 9, 2335 (2018).

    Article  Google Scholar 

  33. Anelli, P. L. et al. Molecular meccano. 1. [2]Rotaxanes and a [2]catenane made to order. J. Am. Chem. Soc. 114, 193–218 (1992).

    Article  CAS  Google Scholar 

  34. Poizat, O., Sourisseau, C. & Mathey, Y. Vibrational study of the methyl viologen dication MV2+ and radical cation MV˙+ in several salts and as an intercalate in some layered MPS3 compounds. J. Chem. Soc. Faraday Trans. 80, 3257–3274 (1984).

    Article  CAS  Google Scholar 

  35. Shearer, C. J., Slattery, A. D., Stapleton, A. J., Shapter, J. G. & Gibson, C. T. Accurate thickness measurement of graphene. Nanotechnology 27, 125704 (2016).

    Article  Google Scholar 

Download references

Acknowledgements

K.P.L. acknowledges NRF-CRP grant “Two-Dimensional Covalent Organic Framework: Synthesis and Applications,” grant number NRF-CRP16-2015-02, funded by National Research Foundation, Prime Minister’s Office, Singapore. We acknowledge the use of the imaging facilities at the Center for BioImaging Sciences. Funding for the K2-IS camera is provided by the Singapore National Research Foundation’s Competitive Research Program (NRF-CRP16-2015-05). We thank S. Xiangyan for the solid-state NMR measurement. We thank C. Hyun and T. J. Shin for the synchrotron-based GIXRD measurements.

Author information

Authors and Affiliations

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

    Xing Li, Hai-Sen Xu, Kai Leng, Xiaoxu Zhao, Hai Xu, Qiang Gao, In-Hyeok Park & Kian Ping Loh

  2. Department of Physics, National University of Singapore, Singapore, Singapore

    See Wee Chee, Noopur Jain, Su Ying Quek & Utkur Mirsaidov

  3. Centre for BioImaging Sciences, Department of Biological Sciences, National University of Singapore, Singapore, Singapore

    See Wee Chee, Noopur Jain & Utkur Mirsaidov

  4. Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, Singapore

    Jingsi Qiao & Su Ying Quek

Authors
  1. Xing Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hai-Sen Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kai Leng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. See Wee Chee
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiaoxu Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Noopur Jain
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hai Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jingsi Qiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Qiang Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. In-Hyeok Park
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Su Ying Quek
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Utkur Mirsaidov
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Kian Ping Loh
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Under the supervision of K.P.L., X.L. designed and performed most of the experiments, including synthesis and characterization of COFs and their model compounds. X.L., H.-S.X. and Q.G. discussed the manuscript. K.L. performed the AFM measurements. Under the supervision of U.M., S.W.C. performed and analysed the TEM of COFs, and N.J. performed and analysed SAED of COFs. X.Z. analysed the TEM results. H.X. performed the Q-plus AFM measurement. Under the supervision of S.Y.Q., J.Q. performed the DFT theoretical calculations. I.-H.P. resolved the single-crystal structures of the model compounds. X.L. and K.P.L. co-wrote the manuscript.

Corresponding author

Correspondence to Kian Ping Loh.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Supplementary information

Supplementary Information

Supplementary text, Figs. 1–35

Supplementary Table 1

Supplementary Tables 1–7

Supplementary Data 2

Single-crystal file of Cy1-MVPF6

Supplementary Data 3

Single-crystal file of CyHz0-MVPF6

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, X., Xu, HS., Leng, K. et al. Partitioning the interlayer space of covalent organic frameworks by embedding pseudorotaxanes in their backbones. Nat. Chem. 12, 1115–1122 (2020). https://doi.org/10.1038/s41557-020-00562-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-020-00562-5

This article is cited by

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