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Hybrid organic–inorganic rotaxanes and molecular shuttles

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.

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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.

References

  1. 1

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

    ADS  CAS  Article  Google Scholar 

  2. 2

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

    CAS  Article  Google Scholar 

  3. 3

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

    CAS  Article  Google Scholar 

  4. 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)

    CAS  Article  Google Scholar 

  5. 5

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

    Article  Google Scholar 

  6. 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. 7

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

  8. 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)

    ADS  CAS  Article  Google Scholar 

  9. 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)

    CAS  Article  Google Scholar 

  10. 10

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

    CAS  Article  Google Scholar 

  11. 11

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

    ADS  Article  Google Scholar 

  12. 12

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

    ADS  CAS  Article  Google Scholar 

  13. 13

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

    CAS  Article  Google Scholar 

  14. 14

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

    ADS  CAS  Article  Google Scholar 

  15. 15

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

    CAS  Article  Google Scholar 

  16. 16

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

    ADS  CAS  Article  Google Scholar 

  17. 17

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

    ADS  CAS  Article  Google Scholar 

  18. 18

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

    CAS  Article  Google Scholar 

  19. 19

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

    CAS  Article  Google Scholar 

  20. 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. 21

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

  22. 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)

    CAS  Article  Google Scholar 

  23. 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. 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)

    CAS  Article  Google Scholar 

  25. 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)

    CAS  Article  Google Scholar 

  26. 26

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

    CAS  Article  Google Scholar 

  27. 27

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

    CAS  Article  Google Scholar 

  28. 28

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

    CAS  Article  Google Scholar 

  29. 29

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

    CAS  Article  Google Scholar 

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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.

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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).

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

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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

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