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DOI: 10.1039/A902818H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2133-2140

The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals

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John D. Holbrey and Kenneth R. Seddon

Abstract

Air- and water-stable 1-alkyl-3-methylimidazolium tetrafluoroborate salts with the general formula [Cn-mim][hair space][BF4] (n = 0–18) have been prepared by metathesis from the corresponding chloride or bromide salts. The salts have been characterised by 1H NMR and IR spectroscopy, microanalysis, polarising optical microscopy and differential scanning calorimetry. Those with short alkyl chains (n = 2–10) are isotropic ionic liquids at room temperature and exhibit a wide liquid range, whereas the longer chain analogues are low melting mesomorphic crystalline solids which display an enantiotropic smectic A mesophase. The thermal range of the mesophase increases with increasing chain length and in the case of the longest chain salt prepared, [C18-mim][BF4], the mesophase range is ca. 150 °C.

References

  1. C. L. Hussey, Adv. Molten Salt Chem., 1983, 5, 185 Search PubMed.
  2. C. L. Hussey, Pure Appl. Chem., 1988, 60, 1763 CrossRef CAS.
  3. K. R. Seddon, Molten Salt Forum, 1998, 5, 53 Search PubMed.
  4. M. Freemantle, Chem. Eng. News, 1998, 76, 32.
  5. J. S. Wilkes and M. J. Zaworotko, J. Chem. Soc., Chem. Commun., 1992, 965 RSC.
  6. E. I. Cooper and E. J. M. O'Sullivan, in Molten Salts, eds. R. J. Gale, G. Blomgren and H. Kojima, The Electrochemical Society Proceedings Series, Pennington, NJ, 1992, vol. 16, p. 386 Search PubMed.
  7. P. Bonhôte, A. P. Diaz, N. Papageorgiou, K. Kalyanasundaram and M. Grätzel, Inorg. Chem., 1996, 35, 1168 CrossRef CAS.
  8. M. Fields, F. V. Hutson, K. R. Seddon and C. M. Gordon, World Pat., WO 98/06106, 1998 Search PubMed.
  9. Y. Chauvin, Actual. Chem., 1996, 7, 44 Search PubMed.
  10. Y. Chauvin, L. Mussmann and H. Olivier, Angew. Chem., Int. Ed. Engl., 1995, 34, 2698 CrossRef.
  11. P. A. Z. Suarez, J. E. L. Dullius, S. Einloft, R. F. de Souza and J. Dupont, Polyhedron, 1996, 1217 CrossRef CAS; A. L. Monteiro, F. K. Zinn, R. F. de Souza and J. Dupont, Tetrahedron-Asymmetry, 1997, 8, 177 Search PubMed; P. A. Z. Suarez, J. E. L. Dullius, S. Einloft, R. F. de Souza and J. Dupont, Inorg. Chim. Acta, 1997, 255, 207 CrossRef CAS.
  12. C. Nanjundiah, S. F. McDevitt and V. R. Koch, J. Electrochem. Soc., 1997, 144, 3392 CAS.
  13. P. A. Z. Suarez, V. M. Selbach, J. E. L. Dullius, S. Einloft, C. M. S. Piatnicki, D. S. Azambuja, R. F. de Souza and J. Dupont, Electrochim. Acta, 1997, 42, 2533 CrossRef CAS; P. A. Z. Suarez, S. Einloft, J. E. L. Dullius, R. F. de Souza and J. Dupont, J. Chim. Phys., 1998, 95, 1626 CAS.
  14. P. Bonhôte, A. P. Dias, N. Papageorgiou, K. Kalyanasundaram and M. Grätzel, Inorg. Chem., 1996, 35, 1168 CrossRef CAS.
  15. See for example, http://www.ch.qub.ac.uk/staff/personal/krs/recent_papers.html.
  16. C. J. Bowlas, D. W. Bruce and K. R. Seddon, Chem. Commun., 1996, 1625 RSC.
  17. C. M. Gordon, J. D. Holbrey, A. R. Kennedy and K. R. Seddon, J. Mater. Chem., 1998, 8, 2627 RSC.
  18. K. M. Lee, C. K. Lee and I. J. B. Lin, Chem. Commun., 1997, 899 RSC.
  19. K. R. Seddon, J. Chem. Technol. Biotechnol., 1997, 68, 351 CrossRef CAS.
  20. S. Christie, S. Subramanian, L. Wang and M. J. Zaworotko, Inorg. Chem., 1993, 32, 5415 CrossRef CAS.
  21. J. Fuller, R. T. Carlin, H. C. De Long and D. Haworth, J. Chem. Soc., Chem. Commun., 1994, 299 RSC.
  22. J. E. L. Dullius, P. A. Z. Suarez, S. Einloft, R. F. de Souza, J. Dupont, J. Fischer and A. De Cian, Organometallics, 1998, 17, 815 CrossRef CAS.
  23. A. Seidell, Solubilities of Inorganic and Metal-organic Compounds, American Chemical Society, Washington DC, 1995, vol. II Search PubMed.
  24. J. Fuller, R. T. Carlin and R. A. Osteryoung, J. Electrochem. Soc., 1997, 144, 3881 CAS.
  25. K. R. Seddon, M. J. Torres and A. Stark, unpublished results.
  26. A. Elaiwi, P. B. Hitchcock, K. R. Seddon, N. Srinivasan, Y.-M. Tan, T. Welton and J. A. Zora, J. Chem. Soc., Dalton Trans., 1995, 3467 RSC.
  27. A. A. Fannin, L. A. King, J. S. Landers, B. J. Piersma, D. J. Stech, R. L. Vaughan and J. S. Wilkes, J. Phys. Chem., 1986, 88, 2614.
  28. G. W. Gray and J. W. Goodby, Smectic Liquid Crystals, Textures and Structures, Leonard Hill, Glasgow, 1984 Search PubMed.
  29. P. A. Winsor, in Liquid Crystals and Plastic Crystals, eds. G. W. Gray and P. A. Winsor, Ellis Horwood, Chichester, 1974, vol. 1, pp. 199–287 Search PubMed.
  30. G. J. T. Tiddy, Phys. Rep., 1980, 57, 1 CrossRef CAS.
  31. A. Skoulis and V. Luzzati, Acta Crystallogr., 1961, 14, 278 CrossRef CAS.
  32. V. Busico, P. Cernicchiaro, P. Corradini and M. Vacatello, J. Phys.Chem., 1983, 87, 1631 CrossRef CAS.
  33. A. C. S. Lawrence, in Liquid Crystals 2, ed. G. H. Brown, Gordon and Breach, London, 1969, part 1, p. 1 Search PubMed.
  34. J. D. Holbrey and K. R. Seddon, unpublished observations.
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