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Coordinated proton tunnelling in a cyclic network of four hydrogen bonds in the solid state

Nature volume 397, pages 241–243 (1999)Cite this article

Abstract

The transfer of protons involved in hydrogen bonding is fundamental to many chemical and biological processes. Quantum tunnelling can play an important role in this process1,2. It manifests itself in strong isotope effects3,4 and has been observed directly in the solid state5. The tunnelling behaviour seen in such studies usually displays the characteristics of a particle confined in a double-well potential. But proton tunnelling can also occur in a coordinated fashion that involves many hydrogen bonds simultaneously. Such a process may significantly affect the properties of linear and circular networks of hydrogen bonds, which occur in ice and in macromolecules containing hydroxyl groups6,7. Here we report the direct observation by NMR relaxometry of coordinated proton tunnelling in a cyclic array of four hydrogen bonds in solid p-tert-butyl calix[4]arene at low temperature. We are able to quantify the parameters that describe this phenomenon and find good agreement with theoretical predictions for phonon-assisted tunnelling8.

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Figure 1: Coordinated proton tunnelling in p-tert-butyl calix[4]arene.
Figure 2: The inverse of the proton spin–lattice relaxation time (T1−1) as a function of the angular frequency ω, at selected temperatures T.
Figure 3: The temperature-dependence of the spectral density amplitude, Cpapb, for the proton transfer motion.

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References

  1. Liu, K. et al. Characterisation of a cage form of the water hexamer. Nature 381, 501–503 (1996).

    Article  ADS  CAS  Google Scholar 

  2. MacGillivray, L. R. & Atwood, J. L. Achiral spherical molecular assembly held together by 60 hydrogen bonds. Nature 389, 469–472 (1997).

    Article  ADS  CAS  Google Scholar 

  3. Bahnson, B. J. et al. Alink between protein structure and enzyme catalyzed hydrogen tunneling. Proc. Natl Acad. Sci. USA 94, 12797–12802 (1997).

    Article  ADS  CAS  Google Scholar 

  4. Aguilar-Parrila, F., Klein, O., Elgeuro, J. & Limbach, H. H. Adynamic 15N NMR study of kinetic hydrogen/deuterium isotope and tunnel effects on the triple proton transfer in crystalline 3,5-dimethylpyrazole. Ber. Bunsenges. Phys. Chem. 101, 889–901 (1997).

    Article  Google Scholar 

  5. Oppenländer, A., Rambaud, C., Trommsdorff, H. P. & Vial, J. C. Translational tunnelling of protons in benzoic-acid crystals. Phys. Rev. Lett. 63, 1432–1435 (1989).

    Article  ADS  Google Scholar 

  6. Saenger, W. Circular hydrogen bonds. Nature 279, 343–344 (1979).

    Article  ADS  CAS  Google Scholar 

  7. Saenger, W., Betzel, Ch., Hingerty, B. & Brown, G. M. Flip-flop hydrogen bonding in a partially disordered system. Nature 296, 581–583 (1982).

    Article  ADS  CAS  Google Scholar 

  8. Skinner, J. L. & Trommsdorff, H. P. Proton transfer in benzoic acid crystals: A chemical spin-boson problem. Theoretical analysis of nuclear magnetic resonance, neutron scattering, and optical experiments. J. Chem. Phys. 89, 897–907 (1988).

    Article  ADS  CAS  Google Scholar 

  9. Diamond, D. & McKervey, M. A. Calixarene-based sensing agents. Chem. Soc. Rev. 25, 15–24 (1996).

    Article  CAS  Google Scholar 

  10. Andreetti, G. D., Ungaro, R. & Pochini, A. Crystal and molecular structure of cyclo{quarter[(5-t-butyl-2-hydroxy-1,3-phenylene)methylene]}toluene (1:1) clathrate. J. Chem. Soc. Chem. Commun. 1005–1007 (1979).

  11. Andrew, E. R. & Latanowicz, L. Solid-state proton transfer dynamics and the proton NMR second moment and proton relaxation rates. J. Magn. Reson. 68, 232–239 (1986).

    ADS  Google Scholar 

  12. Brougham, D. F., Horsewill, A. J. & Jenkinson, R. I. Proton transfer dynamics in the hydrogen bond: adirect measurement of the incoherent tunnelling rate by NMR and the quantum-to-classical transition. Chem. Phys. Lett. 272, 69–74 (1997).

    Article  ADS  CAS  Google Scholar 

  13. Landau, L. D. & Lifshitz, E. M. Quantum Mechanics 177 (Pergamon, Oxford, (1958)).

    MATH  Google Scholar 

Download references

Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) and the Istituto Nazionale per la Fisica della Materia.

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Authors and Affiliations

  1. School of Physics and Astronomy, University of Nottingham, Nottingham, NG7 2RD, UK

    Dermot F. Brougham & Anthony J. Horsewill

  2. Dipartimento di Scienze dei Materiali e della Terra, Istituto Nazionale per la Fisica della Materia, Universit di Ancona, Via Brecce Bianche, I-60131, Ancona, Italy

    Roberto Caciuffo

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  1. Dermot F. Brougham
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Correspondence to Anthony J. Horsewill.

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Brougham, D., Caciuffo, R. & Horsewill, A. Coordinated proton tunnelling in a cyclic network of four hydrogen bonds in the solid state. Nature 397, 241–243 (1999). https://doi.org/10.1038/16672

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