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:

An antiaromatic-walled nanospace

Nature volume 574, pages 511–515 (2019)Cite this article

Subjects

Abstract

Over the past few decades, several molecular cages, hosts and nanoporous materials enclosing nanometre-sized cavities have been reported1,2,3,4,5, including coordination-driven nanocages6. Such nanocages have found widespread use in molecular recognition, separation, stabilization and the promotion of unusual chemical reactions, among other applications3,4,5,6,7,8,9,10. Most of the reported nanospaces within molecular hosts are confined by aromatic walls, the properties of which help to determine the host–guest behaviour. However, cages with nanospaces surrounded by antiaromatic walls have not yet been developed, owing to the instability of antiaromatic compounds; as such, the effect of antiaromatic walls on the properties of nanospaces remains unknown. Here we demonstrate the construction of an antiaromatic-walled nanospace within a self-assembled cage composed of four metal ions with six identical antiaromatic walls. Calculations indicate that the magnetic effects of the antiaromatic moieties surrounding this nanospace reinforce each other. This prediction is confirmed by 1H nuclear magnetic resonance (NMR) signals of bound guest molecules, which are observed at chemical shift values of up to 24 parts per million (ppm), owing to the combined antiaromatic deshielding effect of the surrounding rings. This value, shifted 15 ppm from that of the free guest, is the largest 1H NMR chemical shift displacement resulting from an antiaromatic environment observed so far. This cage may thus be considered as a type of NMR shift reagent, moving guest signals well beyond the usual NMR frequency range and opening the way to further probing the effects of an antiaromatic environment on a nanospace.

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: Cartoon representations of nanospaces.
Fig. 2: Synthesis and NMR characterization of 3.
Fig. 3: Crystal structure of 3 and NICS calculations.
Fig. 4: Host–guest chemistry within antiaromatic-walled nanospace.

Similar content being viewed by others

Data availability

All data needed to evaluate the conclusions given in the paper are present in the paper and Supplementary Information. Any additional data related to this paper may be requested from the authors. Crystallographic data for the structure reported in this paper has been deposited at the Cambridge Crystallographic Data Centre (deposition number 1893553) and can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.

References

  1. Corma, A. State of the art and future challenges of zeolites as catalysts. J. Catal. 216, 298–312 (2003).

    Article  CAS  Google Scholar 

  2. Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).

    Article  CAS  Google Scholar 

  3. Hooley, R. J. & Rebek, J. Jr Chemistry and catalysis in functional cavitands. Chem. Biol. 16, 255–264 (2009).

    Article  CAS  Google Scholar 

  4. Zhang, G. & Mastalerz, M. Organic cage compounds – from shape-persistency to function. Chem. Soc. Rev. 43, 1934–1947 (2014).

    Article  CAS  Google Scholar 

  5. Cook, T. R., Zheng, Y.-R. & Stang, P. J. Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem. Rev. 113, 734–777 (2013).

    Article  CAS  Google Scholar 

  6. Fujita, M. et al. Self-assembly of ten molecules into nanometre-sized organic host frameworks. Nature 378, 469–471 (1995).

    Article  CAS  ADS  Google Scholar 

  7. Ariga, K., Ito, H., Hill, J. P. & Tsukube, H. Molecular recognition: from solution science to nano/materials technology. Chem. Soc. Rev. 41, 5800–5835 (2012).

    Article  CAS  Google Scholar 

  8. Galan, A. & Ballester, P. Stabilization of reactive species by supramolecular encapsulation. Chem. Soc. Rev. 45, 1720–1737 (2016).

    Article  CAS  Google Scholar 

  9. Yoshizawa, M., Klosterman, J. K. & Fujita, M. Functional molecular flasks: new properties and reactions within discrete, self-assembled hosts. Angew. Chem. Int. Ed. 48, 3418–3438 (2009).

    Article  CAS  Google Scholar 

  10. Yoshizawa, M. & Yamashina, M. Coordination-driven nanostructures with polyaromatic shells. Chem. Lett. 46, 163–171 (2017).

    Article  CAS  Google Scholar 

  11. Mugridge, J. S., Bergman, R. G. & Raymond, K. N. 1H NMR chemical shift calculations as a probe of supramolecular host–guest geometry. J. Am. Chem. Soc. 133, 11205–11212 (2011).

    Article  CAS  Google Scholar 

  12. Garcia-Borràs, M., Osuna, S., Luis, J. M., Swart, M. & Solà, M. The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes. Chem. Soc. Rev. 43, 5089–5105 (2014).

    Article  Google Scholar 

  13. Nakamura, Y. et al. A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core. J. Am. Chem. Soc. 128, 4119–4127 (2006).

    Article  CAS  Google Scholar 

  14. Peeks, M. D., Claridge, T. D. W. & Anderson, H. L. Aromatic and antiaromatic ring currents in a molecular nanoring. Nature 541, 200–203 (2017).

    Article  CAS  ADS  Google Scholar 

  15. Breslow, R. Antiaromaticity. Acc. Chem. Res. 6, 393–398 (1973).

    Article  CAS  Google Scholar 

  16. Nishinaga, T., Ohmae, T. & Iyoda, M. Recent studies on the aromaticity and antiaromaticity of planar cyclooctatetraene. Symmetry (Basel) 2, 76–97 (2010).

    Google Scholar 

  17. Zeng, Z. et al. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals. Chem. Soc. Rev. 44, 6578–6596 (2015).

    Article  CAS  Google Scholar 

  18. Hensel, T., Anderson, N. N., Plesner, M. & Pittelkow, M. Synthesis of heterocyclic [8]circulenes and related structures. Synlett 27, 498–525 (2016).

    CAS  Google Scholar 

  19. Reddy, B. K., Basavarajappa, A., Ambhore, M. D. & Anand, V. G. Isophlorinoids: the antiaromatic congeners of porphyrinoids. Chem. Rev. 117, 3420–3443 (2017).

    Article  CAS  Google Scholar 

  20. Szyszko, B., Białek, M. J., Pacholska-Dudziak, E. & Latos-Grażyński, L. Flexible porphyrinoids. Chem. Rev. 117, 2839–2909 (2017).

    Article  CAS  Google Scholar 

  21. Ito, T., Hayashi, Y., Shimizu, S., Shin, J.-Y., Kobayashi, N. & Shinokubo, H. Gram-scale synthesis of nickel(ii) norcorrole: the smallest antiaromatic porphyrinoid. Angew. Chem. Int. Ed. 51, 8542–8545 (2012).

    Article  CAS  Google Scholar 

  22. Deng, Z., Li, X., Stępień, M. & Chmielewski, P. J. Nitration of norcorrolatonickel(ii): first observation of a diatropic current in a system comprising a norcorrole ring. Chem. Eur. J. 22, 4231–4246 (2016).

    Article  CAS  Google Scholar 

  23. Nozawa, R. et al. Stacked antiaromatic porphyrins. Nat. Commun. 7, 13620 (2016).

    Article  CAS  ADS  Google Scholar 

  24. Yoshida, T. & Shinokubo, H. Direct amination of antiaromatic Niii norcorrole. Mater. Chem. Front. 1, 1853–1857 (2017).

    Article  CAS  Google Scholar 

  25. Li, X., Meng, Y., Yi, P., Stępień, M. & Chmielewski, P. J. Pyridine-fused bis(norcorrole) through Hantzsch-type cyclization: enhancement of antiaromaticity by an aromatic bridge. Angew. Chem. Int. Ed. 56, 10810–10814 (2017).

    Article  CAS  Google Scholar 

  26. Kawashima, H., Hiroto, S. & Shinokubo, H. Acid-mediated migration of bromide in an antiaromatic porphyrinoid: preparation of two regioisomeric Ni(ii) bromonorcorroles. J. Org. Chem. 82, 10425–10432 (2017).

    Article  CAS  Google Scholar 

  27. Zhang, D., Ronson, T. K. & Nitschke, J. R. Functional capsules via subcomponent self-assembly. Acc. Chem. Res. 51, 2423–2436 (2018).

    Article  CAS  Google Scholar 

  28. Rizzuto, F. J., Wood, D. M., Ronson, T. K. & Nitschke, J. R. Tuning the redox properties of fullerene clusters within a metal−organic capsule. J. Am. Chem. Soc. 139, 11008–11011 (2017).

    Article  CAS  Google Scholar 

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

    Article  CAS  ADS  Google Scholar 

  30. Brock-Nannestad, T. et al. Tetra-tert-butyltetraoxa[8]circulene and its unusual aggregation behaviour. Eur. J. Org. Chem., 6320–6325 (2011).

Download references

Acknowledgements

This study was supported by the European Research Council (695009) and the UK Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1). M.Y. acknowledges the Japan Society for the Promotion of Science (JSPS) for an Overseas Research Fellowship. R.L. was funded by a Fondation Wiener-Anspach postdoctoral fellowship. M.P. acknowledges support from the Danish Council for Independent Research (DFF 4181-00206). We thank the NMR service of the University of Cambridge Chemistry Department for NMR experiments. We thank Diamond Light Source for providing time on Beamline I19 (MT15768), and D. Allan and L. Saunders for assistance. The computations were performed at the Research Center for Computational Science, Okazaki, Japan. We appreciate discussions with H. Shinokubo (Nagoya University), M. Yoshizawa (Tokyo Institute of Technology) and T. Soya (Kyoto University).

Author information

Author notes

  1. Masahiro Yamashina

    Present address: Department of Chemistry, School of Science, Tokyo Institute of Technology, Tokyo, Japan

Authors and Affiliations

  1. Department of Chemistry, University of Cambridge, Cambridge, UK

    Masahiro Yamashina, Roy Lavendomme, Tanya K. Ronson & Jonathan R. Nitschke

  2. Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Yokohama, Japan

    Yuya Tanaka

  3. Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Michael Pittelkow

Authors
  1. Masahiro Yamashina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuya Tanaka
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Roy Lavendomme
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tanya K. Ronson
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Michael Pittelkow
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jonathan R. Nitschke
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.Y. and J.R.N. designed the work, carried out research, analysed data and wrote the paper. Y.T. contributed to theoretical calculations. R.L. contributed to data analyses and calculations. T.K.R. contributed to X-ray crystallographic analysis. M.P. synthesized tetraoxa[8]circulene. J.R.N. is the principal investigator. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Jonathan R. Nitschke.

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.

Extended data figures and tables

Extended Data Fig. 1 Preparation of diamine 2 from norcorrole 1.

When 1 was treated with 1,3-dibromo-5,5-dimethylhydantoin, inseparable mono-, di- and tribrominated products were obtained. As bromination randomly occurred at positions 3, 7, 12 and 16 (that is, adjacent to the mesityl moieties), the 3,12- and 3,16-substituted dibromonorcorroles trans-1a and cis-1a were obtained as the main products (Supplementary Figs. 1, 2). Subsequently, disubstituted trans-1b and cis-1b were obtained by Suzuki–Miyaura cross-coupling at 43% yield as a mixture of two regioisomers (Supplementary Figs. 3, 4). Finally, 3,12-substituted subcomponent 2 could be isolated as a single regioisomer at 46% yield following reduction of the NO2 groups and chromatography (Supplementary Figs. 5–9). Reagents and conditions: (i) 1,3-dibromo-5,5-dimethylhydantoin, CH2Cl2, −78 °C, 1 h, 94% (mixture of trans-1a, cis-1a and other brominated species). (ii) 4-Nitrophenylboronic acid pinacol ester, Pd(PPh3)4, K3PO4, dry THF, 70 °C, 1 h, 43% (mixture of trans-1b and cis-1b). (iii) SnCl2·H2O, dry THF, 70 °C, overnight, 46% (isolated 2).

Supplementary information

Supplementary Information

This file contains detailed additional synthetic procedures, host–guest studies, extended methods, full characterisation data, Supplementary Figures 1–74, Supplementary Tables 1–7 and additional references – see content page for details.

Supplementary Data

This file contains the crystallographic data for compound 3.

Video 1

Three-dimensional NICSiso grid within the antiaromatic-walled nanospace. Yellow, orange and red dots represent medium to strong magnetic deshielding regions (NICSiso = 3–6 for yellow, 6–9 for orange and >9 for red). Regions outside the walls and for NICSiso<3 are not shown for clarity. Calculation details are provided in the Supplementary Information.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yamashina, M., Tanaka, Y., Lavendomme, R. et al. An antiaromatic-walled nanospace. Nature 574, 511–515 (2019). https://doi.org/10.1038/s41586-019-1661-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-019-1661-x

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

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