Thermodynamic study of p-sulfonated calixarene complexes in aqueous solution

Abstract

Association equilibrium constants and thermodynamic parameters (i.e., ΔH and ΔS ) for complexation between N,N-dimethylindoaniline and p-sulfonated calix[n]arenes in aqueous solution have been determined by means of UV–VIS spectroscopy. Equilibrium constants corresponding to calix[n]arene-p-sulfonates increase in the order [4] < [6] ≈ [8]. ΔH and ΔS values, which are interpreted in terms of the importance of the various interactions responsible for complexation, lead to a linear ΔH – TΔS relationship. Such a linear correlation is interpreted in terms of the extent of calixarene conformational change and of host and guest desolvation involved in the complexation process.

References

1. M. L. Bender and M. Komiyama, Cyclodextrin chemistry, Springer Verlag, Berlin, 1978.
2. J. Szejtli, Cyclodextrins and their inclusion complexes, Akadémiai Kiadó, Budapest, 1982.
3. J. Vincens and V. Böhmer, Calixarenes: a versatile class of macrocyclic compounds, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1991, vol. 3.
4. C. D. Gutsche and I. Alam, Tetrahedron, 1988, 44, 4689.
5. S. Shinkai, K. Araki and O. Manabe, J. Am. Chem. Soc., 1988, 110, 7214.
6. S. Shinkai, H. Kawabata, T. Arimura, T. Matsuda, H. Satoh and O. Manabe, J. Chem. Soc., Perkin Trans. 1, 1989, 1073.
7. S. Shinkai, K. Araki, T. Matsuda and O. Manabe, Bull. Chem. Soc. Jpn., 1989, 62, 3856.
8. T. Arimura, T. Nagasaki, S. Shinkai and T. Matsuda, J. Org. Chem., 1989, 54, 3766.
9. I. Alam and C. D. Gutsche, J. Org. Chem., 1990, 55, 4487.
10. T. Nagasaki, Y. Tajiri and S. Shinkai, Recl. Trav. Chim. Pays-Bas, 1993, 112, 407.
11. Y. Shi, D. Wang and Z. Zhang, J. Photochem. Photobiol., A: Chem., 1995, 91, 211.
12. Y. Zhang, R. A. Agbaria and I. M. Warner, Supramol. Chem., 1997, 8, 309.
13. S. Shinkai, S. Mori, T. Tsubaki, T. Sone and O. Manabe, Tetrahedron Lett., 1984, 25, 5315.
14. S. Shinkai, S. Mori, H. Koreishi, T. Tsubaki and O. Manabe, J. Am. Chem. Soc., 1986, 108, 2409.
15. S. Shinkai, Pure Appl. Chem., 1986, 58, 1523.
16. C. Reichardt, Solvents and solvent effects in organic chemistry, VCH, Weinheim, Germany, 1990.
17. Y. Inoue, T. Hakushi, Y. Liu, L.-H. Tong, B.-J. Shen and D.-S. Jin, J. Am. Chem. Soc., 1993, 115, 475.
18. Y. Inoue, Y. Liu, L.-H. Tong, B.-J. Shen and D.-S. Jin, J. Am. Chem. Soc., 1993, 115, 10 637.
19. S. Shinkai, T. Arimura, K. Araki, H. Kawabata, H. Satoh, T. Tsubaki, O. Manabe and J. Sunamoto, J. Chem. Soc., Perkin Trans. 1, 1989, 2039.
20. Y. Inoue and T. Hakushi, J. Chem. Soc., Perkin Trans. 2, 1985, 935.
21. Y. Liu, L.-H. Tong, S. Huang, B.-Z. Tian, Y. Inoue and T. Hakushi, J. Phys. Chem., 1990, 94, 2666.
22. K. Araki, H. Shimizu and S. Shinkai, Chem. Lett., 1993, 205.
23. W. L. Jorgensen, T. B. Nguyen, E. M. Sanford, I. Chao, K. N. Houk and F. J. Diederich, J. Am. Chem. Soc., 1992, 114, 4003.
24. C. D. Gutsche and L.-G. Lin, Tetrahedron, 1986, 42, 1633.
25. S. Shinkai, K. Araki, T. Tsubaki, T. Arimura and O. Manabe, J. Chem. Soc., Perkin Trans. 1, 1987, 2297.