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:

Active template strategy for the preparation of π-conjugated interlocked nanocarbons

Nature Chemistry volume 15, pages 170–176 (2023)Cite this article

Subjects

Abstract

Mechanically interlocked carbon nanostructures represent a relatively unexplored frontier in carbon nanoscience due to the difficulty in preparing these unusual topological materials. Here we illustrate an active-template method in which a [n]cycloparaphenylene precursor macrocycle is decorated with two convergent pyridine donors that coordinate to a metal ion. The metal ion catalyses alkyne–alkyne cross-coupling reactions within the central cavity of the macrocycle, and the resultant interlocked products can be converted into fully π-conjugated structures in subsequent synthetic steps. Specifically, we report the synthesis of a family of catenanes that comprise two or three mutually interpenetrating [n]cycloparaphenylene-derived macrocycles of various sizes. Additionally, a fully π-conjugated [3]rotaxane was synthesized by the same method. The development of synthetic methods to access mechanically interlocked carbon nanostructures of varying topology can help elucidate the implications of mechanical bonding for this emerging class of nanomaterials and allow structure–property relationships to be established.

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: Methods to synthesize π-conjugated interlocked nanocarbon species.
Fig. 2: Preparation of π-conjugated catenanes.
Fig. 3: X-ray structures of 1a, 1b and 2.
Fig. 4: Synthesis of a fully π-conjugated [3]rotaxane.
Fig. 5: Photophysical characteristics of compounds.
Fig. 6: Effect of N-atom positioning on the AT reaction.

Similar content being viewed by others

Data availability

Experimental procedures for the synthesis of all the compounds are available in the Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2159304 (1a), 2159303 (1b), 2159302 (2), 2159305 (diaza[8]CPP) and 2159306 (diaza[9]CPP). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. In addition to the spectra provided in the Supplementary Information, raw 1H and 13C data for all the novel structures are provided as Supplementary Data 6.

References

  1. Thomas, S., Sarathchandran, C., Ilangovan, S. A. and Moreno-Pirajan, J. C. Handbook of Carbon-Based Nanomaterials (Elsevier, 2021).

  2. Jasti, R., Bhattacharjee, J., Neaton, J. B. & Bertozzi, C. R. Synthesis, characterization, and theory of [9]-, [12]-, and [18]cycloparaphenylene: carbon nanohoop structures. J. Am. Chem. Soc. 130, 17646–17647 (2008).

    Article  CAS  Google Scholar 

  3. Povie, G., Segawa, Y., Nishihara, T., Miyauchi, Y. & Itami, K. Synthesis of a carbon nanobelt. Science 356, 172–175 (2017).

    Article  CAS  Google Scholar 

  4. Cheung, K. Y. et al. Synthesis of armchair and chiral carbon nanobelts. Chem 5, 838–847 (2019).

    Article  CAS  Google Scholar 

  5. Cheung, K. Y., Watanabe, K., Segawa, Y. & Itami, K. Synthesis of a zigzag carbon nanobelt. Nat. Chem. 13, 255–259 (2021).

    Article  CAS  Google Scholar 

  6. Darzi, E. R., Sisto, T. J. & Jasti, R. Selective syntheses of [7]–[12]cycloparaphenylenes using orthogonal Suzuki–Miyaura cross-coupling reactions. J. Org. Chem. 77, 6624–6628 (2012).

    Article  CAS  Google Scholar 

  7. Lovell, T. C., Colwell, C. E., Zakharov, L. N. & Jasti, R. Symmetry breaking and the turn-on fluorescence of small, highly strained carbon nanohoops. Chem. Sci. 10, 3786–3790 (2019).

    Article  CAS  Google Scholar 

  8. Hermann, M., Wassy, D. & Esser, B. Conjugated nanohoops incorporating donor, acceptor, hetero- or polycyclic aromatics. Angew. Chem. Int. Ed. 60, 15743–15766 (2021).

    Article  CAS  Google Scholar 

  9. Leonhardt, E. J. & Jasti, R. Emerging applications of carbon nanohoops. Nat. Rev. Chem. 3, 672–686 (2019).

    Article  CAS  Google Scholar 

  10. White, B. M. et al. Expanding the chemical space of biocompatible fluorophores: nanohoops in cells. ACS Cent. Sci. 4, 1173–1178 (2018).

    Article  CAS  Google Scholar 

  11. Lovell, T. C. et al. Subcellular targeted nanohoop for one- and two-photon live cell imaging. ACS Nano 15, 15285–15293 (2021).

    Article  CAS  Google Scholar 

  12. Peters, G. M. et al. Linear and radial conjugation in extended π-electron systems. J. Am. Chem. Soc. 142, 2293–2300 (2020).

    Article  CAS  Google Scholar 

  13. Huang, Q. et al. A long π-conjugated poly(para-phenylene)-based polymeric segment of single-walled carbon nanotubes. J. Am. Chem. Soc. 141, 18938–18943 (2019).

    Article  CAS  Google Scholar 

  14. Segawa, Y. et al. Topological molecular nanocarbons: all-benzene catenane and trefoil knot. Science 365, 272–276 (2019).

    Article  CAS  Google Scholar 

  15. Aucagne, V., Hänni, K. D., Leigh, D. A., Lusby, P. J. & Walker, D. B. Catalytic ‘click’ rotaxanes: a substoichiometric metal-template pathway to mechanically interlocked architectures. J. Am. Chem. Soc. 128, 2186–2187 (2006).

    Article  CAS  Google Scholar 

  16. Dietrich-Buchecker, C. O., Sauvage, J. P. & Kintzinger, J. P. Une nouvelle famille de molecules: les metallo-catenanes. Tetrahedron Lett. 24, 5095–5098 (1983).

    Article  CAS  Google Scholar 

  17. Barin, G., Coskun, A., Fouda, M. M. G. & Stoddart, J. F. Mechanically interlocked molecules assembled by π–π recognition. ChemPlusChem. 77, 159–185 (2012).

    Article  CAS  Google Scholar 

  18. Denis, M. & Goldup, S. M. The active template approach to interlocked molecules. Nat. Rev. Chem. 1, 0061 (2017).

    Article  CAS  Google Scholar 

  19. Kubota, N., Segawa, Y. & Itami, K. η6-Cycloparaphenylene transition metal complexes: synthesis, structure, photophysical properties, and application to the selective monofunctionalization of cycloparaphenylenes. J. Am. Chem. Soc. 137, 1356–1361 (2015).

    Article  CAS  Google Scholar 

  20. Van Raden, J. M., Louie, S., Zakharov, L. N. & Jasti, R. 2,2′-Bipyridyl-embedded cycloparaphenylenes as a general strategy to investigate nanohoop-based coordination complexes. J. Am. Chem. Soc. 139, 2936–2939 (2017).

    Article  Google Scholar 

  21. Van Raden, J. M., White, B. M., Zakharov, L. N. & Jasti, R. Nanohoop rotaxanes from active metal template syntheses and their potential in sensing applications. Angew. Chem. Int. Ed. 58, 7341–7345 (2019).

    Article  Google Scholar 

  22. Fan, Y. Y. et al. An isolable catenane consisting of two Möbius conjugated nanohoops. Nat. Commun. 9, 3037 (2018).

    Article  Google Scholar 

  23. Berná, J. et al. Cadiot–Chodkiewicz active template synthesis of rotaxanes and switchable molecular shuttles with weak intercomponent interactions. Angew. Chem. Int. Ed. 47, 4392–4396 (2008).

    Article  Google Scholar 

  24. Movsisyan, L. D. et al. Polyyne rotaxanes: stabilization by encapsulation. J. Am. Chem. Soc. 138, 1366–1376 (2016).

    Article  CAS  Google Scholar 

  25. Hashimoto, S. et al. Synthesis and physical properties of polyfluorinated cycloparaphenylenes. Org. Lett. 20, 5973–5976 (2018).

    Article  CAS  Google Scholar 

  26. Coropceanu, V. et al. Charge transport in organic semiconductors. Chem. Rev. 107, 926–952 (2007).

    Article  CAS  Google Scholar 

  27. Slater, A. G. & Cooper, A. I. Function-led design of new porous materials. Science 348, aaa8075 (2015).

    Article  Google Scholar 

  28. Darzi, E. R. & Jasti, R. The dynamic, size-dependent properties of [5]–[12]cycloparaphenylenes. Chem. Soc. Rev. 44, 6401–6410 (2015).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This project was supported by the National Science Foundation (CHE-1808791). J.H.M. and R.L.M. were additionally supported by National Science Foundation Graduate Research Fellowships.

Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Oregon, USA

    James H. May, Jeff M. Van Raden, Ruth L. Maust & Ramesh Jasti

  2. CAMCOR—Center for Advanced Materials Characterization in Oregon, University of Oregon, Oregon, USA

    Lev N. Zakharov

Authors
  1. James H. May
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jeff M. Van Raden
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ruth L. Maust
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lev N. Zakharov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ramesh Jasti
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.H.M., J.M.V.R. and R.J. were responsible for the conceptualization of the project. All the synthetic steps reported were performed by J.H.M. along with the computational and photophysical analyses. J.H.M. and R.J. drafted the original version of the manuscript with editing from J.M.V.R. and R.L.M. L.N.Z. collected and analysed all the crystallographic data.

Corresponding author

Correspondence to Ramesh Jasti.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Chemistry thanks Birgit Esser and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

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

Supplementary information

Supplementary Information

Experimental Details, NMR spectra of compounds, crystallographic information, computational details, Supplementary Figs. 1–72, discussion and Table 1.

Supplementary Data 1

.cif file for compound 1a.

Supplementary Data 2

.cif file for compound 1b..

Supplementary Data 3

.cif file for compound 2

Supplementary Data 4

.cif file for compound diaza[8]CPP.

Supplementary Data 5

.cif file for compound diaza[9]CPP.

Supplementary Data 6

.zip file containing 1H and 13 C NMR of all reported compounds.

Supplementary Data 7

.out file for the optimized structures of [11 + 2]CPP and [12 + 4]CPP.

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

May, J.H., Van Raden, J.M., Maust, R.L. et al. Active template strategy for the preparation of π-conjugated interlocked nanocarbons. Nat. Chem. 15, 170–176 (2023). https://doi.org/10.1038/s41557-022-01106-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-022-01106-9

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