The structure and thermal behaviour of some long chain cerium(III) carboxylates

Abstract

The even chain length cerium(III) carboxylates from the octanoate to the octadecanoate have been synthesised by metathesis. Thermogravimetry shows the presence of coordinated water for the short chain homologues, whereas the longer chain ones only contain adsorbed water. X-Ray diffraction and IR spectral measurements show that the solid phase has a lamellar, bilayer structure with planes of the cerium(III) ions coordinated to the carboxylate groups. The phase behaviour of the carboxylates has been studied by DSC and polarized-light microscopy. One or more mesophases are observed over the temperature range 70–120°C and melting occurs between 130 and 150°C. The textures observed on the polarizing microscope clearly show the anisotropic nature of the mesophases. Although the overall enthalpy and entropy of melting of these compounds increase with increasing chain length, the values are considerably lower than expected for complete fusion of the alkyl chains. Competition between melting of the chains and changes in the metal–carboxylate coordination region is the major factor responsible for the differences observed in the phase behaviour between the short and long chain derivatives.

References

1. F. J. Buono and M. L. Feldman, Kirk–Othmer Encyclopedia of Chemical Technology, ed. H. F. Mark, D. F. Othmer, C. G. Overberger and G. T. Seaborg, Wiley, New York, 3rd edn., 1979, vol. 8, p. 34.
2. R. G. Bossert, J. Chem. Educ., 1950, 27, 10.
3. M. S. Akanni, E. K. Okoh, H. D. Burrows and H. A. Ellis, Thermochim. Acta, 1992, 208, 1.
4. S. N. Misra, T. N. Misra and R. C. Mehrotra, J. Inorg. Nucl. Chem., 1963, 25, 195.
5. R. C. Mehrotra, T. N. Misra and S. N. Misra, J. Indian Chem. Soc., 1966, 43, 61.
6. R. C. Paul, M. S. Bains and J. S. Gothi, Indian J. Chem., 1969, 7, 514.
7. R. C. Paul, G. Singh and J. C. Ghotra, Indian J. Chem., 1973, 11, 294.
8. R. C. Vickery, J. Mol. Spectrosc., 1958, 2, 308.
9. R. A. Mostyn, B. T. N. Newland and W. E. Hearn, Anal. Chim. Acta, 1970, 51, 520.
10. K. N. Mehrotra, A. S. Gahlaut and M. Sharma, J. Colloid Interface Sci., 1987, 120, 110.
11. K. N. Mehrotra, R. V. Shukla and M. Chauhan, Bull. Electrochem., 1988, 4, 513.
12. K. N. Mehrotra, M. Chauhan and R. K. Shukla, Tenside, Surfactants, Deterg., 1992, 29, 432.
13. K. N. Mehrotra, R. K. Shukla and M. Chauhan, Bull. Chem. Soc. Jpn., 1995, 68, 1825.
14. K. N. Mehrotra, M. Chauhan and R. K. Shukla, Tenside, Surfactants, Deterg., 1996, 33, 319.
15. Y. Lin, J. Rare Earths, 1996, 14, 98.
16. H. A. Ellis and A. DeVries, Mol. Cryst. Liq. Cryst., 1988, 163, 133.
17. R. D. Vold and G. S. Hattiangdi, Ind. Eng. Chem., 1949, 41, 2311.
18. A. M. A. Costa, H. D. Burrows, C. F. G. C. Geraldes, J. J. C. Teixeira-Dias, C. G. Bazuin, D. Guillon, A. Skoulios, E. Blackmore, G. J. T. Tiddy and D. L. Turner, Liq. Cryst., 1986, 1, 215.
19. C. G. Bazuin, D. Guillon, A. Skoulios, A. M. A. Costa, H. D. Burrows, C. F. G. C. Geraldes, J. J. C. Teixeira-Dias, E. Blackmore and G. J. T. Tiddy, Liq. Cryst., 1988, 3, 1655.
20. N. B. Colthup, L. H. Daly and S. E. Wiberly, Introduction to Infrared and Raman Spectroscopy, Academic Press, New York, 1975, p. 223.
21. E. M. Kirby, M. J. Evans-Vader and M. A. Brown, J. Am. Oil Chem. Soc., 1965, 42, 437.
22. D. D. Saperstein, J. Phys. Chem., 1987, 91, 2922.
23. K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds, Wiley, New York, 1963, p. 198.
24. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley, New York, 5th edn., 1988, p. 483.
25. G. B. Deacon and R. J. Phillips, Coord. Chem. Rev., 1980, 33, 227.
26. M. A. Mesubi, J. Mol. Struct., 1982, 81, 61.
27. D. P. Strommen, A.-M. Giroud-Godquin, P. Maldivi, J.-C. Marchon and B. Marchon, Liq. Cryst., 1987, 2, 689.
28. R. A. Meiklejohn, R. J. Meyer, S. M. Aronovic, H. A. Schuette and V. W. Meloch, Anal. Chem., 1957, 29, 329.
29. R. G. Snyder, J. Mol. Spectrosc., 1961, 7, 117.
30. V. P. Mehta, M. Hasan and L. C. Heda, J. Macromol. Sci.-Chem. A, 1982, A17, 113.
31. M. F. R. Moita, M. L. T. S. Duarte and R. Fausto, Spectrosc. Lett., 1994, 27, 1421.
32. D. Chapman, in Colloquium Spectroscopcum Internacionale VI (Amsterdam 1956), ed. W. V. Tongeren, F. Freese and E. H. S. Someren, Pergamon Press, London, 1956, p. 609.
33. G. Blasse, W. Schipper and J. J. Hamelink, Inorg. Chim. Acta, 1991, 189, 77.
34. G. Blasse, G. J. Dirksen, N. Sabbatini and S. Perathoner, Inorg. Chim. Acta, 1988, 133, 167.
35. S. T. Frey and W. DeW. Horrocks, Jr, Inorg. Chem., 1991, 30, 1073.
36. Y. Kaizu, K. Miyakawa, K. Okada, H. Kobayashi, M. Sumitani and K. Yoshihara, J. Am. Chem. Soc., 1985, 107, 2622.
37. P. N. Hazin, C. Lakshminarayan, L. S. Brinen, J. L. Knee, J. W. Bruno, W. E. Streib and K. Folting, Inorg. Chem., 1988, 27, 1393.
38. H. D. Burrows, in The Structure, Dynamics and Equilibrium Properties of Colloidal Systems, ed. D. M. Bloor and E. Wyn-Jones, Kluwer, Dordrecht, 1990, p. 415.
39. M. J. Vold, M. Macomber and R. D. Vold, J. Am. Chem. Soc., 1940, 63, 168.
40. M. L. Phillips and J. Jonas, Liq. Cryst., 1987, 2, 335.
41. J. F. Nagle, Annu. Rev. Phys. Chem., 1980, 31, 157.
42. H. D. Burrows, in Molecular Liquids: New Perspectives in Physics and Chemistry, ed. J. J. C. Teixeira-Dias, Kluwer, Dordrecht, 1992, p. 333.
43. P. Seurin, D. Guillon and A. Skoulios, Mol. Cryst. Liq. Cryst., 1981, 65, 85.
44. Ref. 24, p. 958.
45. G. Zerbi, G. Conti, G. Minoni, S. Pison and A. Bigotto, J. Phys. Chem., 1987, 91, 2386.
46. F. B. Rosevear, J. Am. Oil Chem. Soc., 1954, 31, 628.
47. D. Demus, Z. Chem., 1975, 15, 1 and references therein.
48. D. W. McLure, J. Chem. Phys., 1968, 49, 1830.