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.

  • Letter
  • Published:

Hybrid organic–inorganic rotaxanes and molecular shuttles

Nature volume 458, pages 314–318 (2009)Cite this article

Abstract

The tetravalency of carbon and its ability to form covalent bonds with itself and other elements enables large organic molecules with complex structures, functions and dynamics to be constructed. The varied electronic configurations and bonding patterns of inorganic elements, on the other hand, can impart diverse electronic, magnetic, catalytic and other useful properties to molecular-level structures. Some hybrid organic–inorganic materials that combine features of both chemistries have been developed, most notably metal–organic frameworks1, dense and extended organic–inorganic frameworks2 and coordination polymers3. Metal ions have also been incorporated into molecules that contain interlocked subunits, such as rotaxanes4,5,6,7 and catenanes6,8, and structures in which many inorganic clusters encircle polymer chains have been described9. Here we report the synthesis of a series of discrete rotaxane molecules in which inorganic and organic structural units are linked together mechanically at the molecular level. Structural units (dialkyammonium groups) in dumb-bell-shaped organic molecules template the assembly of essentially inorganic ‘rings’ about ‘axles’ to form rotaxanes consisting of various numbers of rings and axles. One of the rotaxanes behaves as a ‘molecular shuttle’10: the ring moves between two binding sites on the axle in a large-amplitude motion typical of some synthetic molecular machine systems11,12,13,14,15. The architecture of the rotaxanes ensures that the electronic, magnetic and paramagnetic characteristics of the inorganic rings—properties that could make them suitable as qubits for quantum computers16,17,18—can influence, and potentially be influenced by, the organic portion of the molecule.

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

Figure 1: Synthesis and X-ray crystal structure of hybrid organic-inorganic [2]rotaxane 2c.
Figure 2: 1H NMR spectra (500 MHz, C2D2Cl4).
Figure 3: Synthesis of hybrid organic–inorganic [3]rotaxane 5b, [4]rotaxane 6b and molecular shuttle 4a.
Figure 4: X-ray crystal structures.

Similar content being viewed by others

References

  1. Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003)

    Article  ADS  CAS  Google Scholar 

  2. Cheetham, A. K. & Rao, C. N. R. There’s room in the middle. Science 318, 58–59 (2007)

    Article  CAS  Google Scholar 

  3. Kitagawa, S., Kitaura, R. & Noro, S.-i. Functional porous coordination polymers. Angew. Chem. Int. Edn 43, 2334–2375 (2004)

    Article  CAS  Google Scholar 

  4. Ogino, H. Relatively high-yield syntheses of rotaxanes. Syntheses and properties of compounds consisting of cyclodextrins threaded by α, ω-diaminoalkanes coordinated to cobalt(III) complexes. J. Am. Chem. Soc. 103, 1303–1304 (1981)

    Article  CAS  Google Scholar 

  5. Batten, S. R. & Robson, R. Interpenetrating nets: ordered, periodic entanglement. Angew. Chem. Int. Edn 37, 1460–1494 (1998)

    Article  Google Scholar 

  6. Sauvage, J.-P. & Dietrich-Buchecker, C. (eds) Molecular Catenanes, Rotaxanes and Knots: A Journey through the World of Molecular Topology (Wiley-VCH, 1999)

    Book  Google Scholar 

  7. Loeb, S. J. Metal organic rotaxane frameworks. Chem. Commun. 1511–1518 (2005)

  8. Fujita, M., Ibukuro, F., Hagihara, H. & Ogura, K. Quantitative self-assembly of a [2]catenane from two preformed molecular rings. Nature 367, 720–723 (1994)

    Article  ADS  CAS  Google Scholar 

  9. Alam, M. A. et al. Directed 1D assembly of a ring-shaped inorganic nanocluster templated by an organic rigid-rod molecule. Angew. Chem. Int. Edn 47, 2070–2073 (2008)

    Article  CAS  Google Scholar 

  10. Anelli, P. L., Spencer, N. & Stoddart, J. F. A molecular shuttle. J. Am. Chem. Soc. 113, 5131–5133 (1991)

    Article  CAS  Google Scholar 

  11. Berná, J. et al. Macroscopic transport by synthetic molecular machines. Nature Mater. 4, 704–710 (2005)

    Article  ADS  Google Scholar 

  12. Nguyen, T. et al. A reversible molecular valve. Proc. Natl Acad. Sci. USA 102, 10029–10034 (2005)

    Article  ADS  CAS  Google Scholar 

  13. Liu, Y. et al. Linear artificial molecular muscles. J. Am. Chem. Soc. 127, 9745–9759 (2005)

    Article  CAS  Google Scholar 

  14. Green, J. E. et al. A 160-kilobit molecular electronic memory patterned at 1011 bits per square centimetre. Nature 445, 414–417 (2007)

    Article  ADS  CAS  Google Scholar 

  15. Kay, E. R., Leigh, D. A. & Zerbetto, F. Synthetic molecular motors and mechanical machines. Angew. Chem. Int. Edn 46, 72–191 (2007)

    Article  CAS  Google Scholar 

  16. Leuenberger, M. N. & Loss, D. Quantum computing in molecular magnets. Nature 410, 789–793 (2001)

    Article  ADS  CAS  Google Scholar 

  17. Bertaina, S. et al. Quantum oscillations in a molecular magnet. Nature 453, 203–206 (2008)

    Article  ADS  CAS  Google Scholar 

  18. Winpenny, R. E. P. Quantum information processing using molecular nanomagnets as qubits. Angew. Chem. Int. Edn 47, 7992–7994 (2008)

    Article  CAS  Google Scholar 

  19. Larsen, F. K. et al. Synthesis and characterization of heterometallic {Cr7M} wheels. Angew. Chem. Int. Edn 42, 101–105 (2003)

    Article  CAS  Google Scholar 

  20. Affronte, M., Carretta, S., Timco, G. A. & Winpenny, R. E. P. A ring cycle: studies of heterometallic wheels. Chem. Commun. 1789–1797 (2007)

  21. Timco, G. A. et al. Influencing the nuclearity and constitution of heterometallic rings via templates. Chem. Commun. 3649–3651 (2005)

  22. Cador, O. et al. The magnetic Möbius strip: synthesis, structure and magnetic studies of odd-numbered antiferromagnetically coupled wheels. Angew. Chem. Int. Edn 43, 5196–5200 (2004)

    Article  CAS  Google Scholar 

  23. Kolchinski, A. G., Busch, D. H. & Alcock, N. W. Gaining control over molecular threading: benefits of second coordination sites and aqueous–organic interfaces in rotaxane synthesis. J. Chem. Soc. Chem. Commun. 1289–1291 (1995)

  24. Ashton, P. R. et al. Self-assembling [2]- and [3]rotaxanes from secondary dialkylammonium salts and crown ethers. Chem. Eur. J. 2, 729–736 (1996)

    Article  CAS  Google Scholar 

  25. Mock, W. L., Irra, T. A., Wepsiec, J. P. & Adhia, M. Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation. J. Org. Chem. 54, 5302–5308 (1989)

    Article  CAS  Google Scholar 

  26. Kim, K. Mechanically interlocked molecules incorporating cucurbituril and their supramolecular assemblies. Chem. Soc. Rev. 31, 96–107 (2002)

    Article  CAS  Google Scholar 

  27. Aucagne, V., Leigh, D. A., Lock, J. S. & Thomson, A. R. Rotaxanes of cyclic peptides. J. Am. Chem. Soc. 128, 1784–1785 (2006)

    Article  CAS  Google Scholar 

  28. Ashton, P. R. et al. Doubly encircled and double-stranded pseudorotaxanes. Angew. Chem. Int. Edn Engl. 34, 1869–1871 (1995)

    Article  CAS  Google Scholar 

  29. Perrin, C. L. & Dwyer, T. J. Application of two-dimensional NMR to kinetics of chemical exchange. Chem. Rev. 90, 935–967 (1990)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank J. Bella for the exchange spectroscopy NMR experiments, W. Sun for assistance with the preparation of thread 1c and the Engineering and Physical Sciences Research Council (EPSRC) National Mass Spectrometry Service Centre (Swansea, UK) for high-resolution mass spectrometry. This research was funded by the European Commission (through the NoE ‘MAGMANet’) and EPSRC. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. D.S. is a Swiss National Science Foundation postdoctoral fellow. D.A.L. is an EPSRC Senior Research Fellow and holds a Royal Society Wolfson Research Merit Award.

Author Contributions C.-F.L., D.S. and G.A.T. carried out the synthesis and characterization studies, helped plan the experiments and participated in the preparation of the manuscript. R.G.P. and S.J.T. collected the X-ray data and solved the crystal structures. D.A.L. and R.E.P.W. helped plan the experiments and prepare the manuscript.

Author information

Authors and Affiliations

  1. School of Chemistry, University of Edinburgh, The King’s Buildings, West Mains Road, Edinburgh EH9 3JJ, UK,

    Chin-Fa Lee, David A. Leigh & David Schultz

  2. School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK,

    Robin G. Pritchard, Grigore A. Timco & Richard E. P. Winpenny

  3. Advanced Light Source, Lawrence Berkeley Laboratory, 1 Cyclotron Road, MS2-400, Berkeley, California 94720, USA,

    Simon J. Teat

Authors
  1. Chin-Fa Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. David A. Leigh
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Robin G. Pritchard
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. David Schultz
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Simon J. Teat
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Grigore A. Timco
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Richard E. P. Winpenny
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to David A. Leigh or Richard E. P. Winpenny.

Additional information

The crystallographic data and experimental details of the structural refinement for the X-ray crystal structures reported in this paper have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 705132–CCDC 705135. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/data_request/cif).

Supplementary information

Supplementary Information

This file contains Supplementary Notes, Supplementary Figures S1-S11 with Legends and Supplementary Tables S1-S5 (PDF 4727 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Lee, CF., Leigh, D., Pritchard, R. et al. Hybrid organic–inorganic rotaxanes and molecular shuttles. Nature 458, 314–318 (2009). https://doi.org/10.1038/nature07847

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature07847

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