Study on host–guest complexation of anions based on tri-podal naphthylthiourea derivatives

Abstract

A new host tris[N ′-naphthyl-N-(2-aminoethyl)thiourea]amine (3) and the reference compounds bis[N ′-naphthyl-N-(2-aminoethyl)thiourea]amine (2) and N ′-naphthyl-N-n-amylthiourea (1) were synthesized and used for the recognition of anionic species. Considerable changes in UV/Vis absorption of host 3 induced by complexation with H₂PO₄^– (or HSO₄^–) were observed. UV/Vis spectroscopy titration experiments and ¹H-NMR results both indicated the formation of 1∶1 stable complexes between 3 and H₂PO₄^– (or HSO₄^–). The stability constants of the complexes were determined in DMF. The results demonstrate that optically changeable receptors for anions may be constructed by appropriate design of host molecules.

References

1. (a) H. Luecke and F. A. Quiocho, Nature, 1990, 347, 402; (b) J. J. He and F. A. Quiocho, Science, 1991, 251, 1479; (c) E. V. Anslyn, J. Smith, D. M. Kneeland, K. Ariga and F. Chu, Supramol. Chem., 1993, 1, 201.
2. (a) C. Seel and J. de Mendoza, Comprehensive Supramolecular Chemistry, ed. J. M. Lehn, J. L. Atwood, J. E. D. Davies, D. D. MacNicol and F. Vogtle, Pergamon/Elsevier, Oxford, 1996, vol. 2, p. 519; (b) F. P. Schmidtchen and M. Berger, Chem. Rev., 1997, 97, 1609; (c) B. L. Jacobson and F. A. Quiocho, J. Mol. Biol., 1988, 204, 783.
3. (a) E. Kimura, S. Aoki, T. Koike and M. Shiro, J. Am. Chem. Soc., 1997, 119, 3086; (b) K. Niikura, A. Metzger and E. V. Anslyn, J. Am. Chem. Soc., 1998, 120, 8533.
4. P. A. Gale, J. L. Sessler, V. Vrál and V. Lynch, J. Am. Chem. Soc., 1996, 118, 5140.
5. M. T. Reetz, C. M. Miemeyer and K. Harms, Angew. Chem., Int. Ed. Engl., 1991, 30, 1472.
6. (a) Y. Morzherin, D. M. Rudkevich, W. Verboom and D. N. Reinhoudt, J. Org. Chem., 1993, 58, 7602; (b) J. Scheerder, J. F. J. Engbersen, A. Casnati, R. Ungaro and D. N. Reinhoudt, J. Org. Chem., 1995, 60, 6448.
7. (a) S. Valiyaveettil, J. F. J. Engbersen, W. Verboom and D. N. Reinhoudt, Angew. Chem., Int. Ed. Engl., 1993, 32, 942; (b) P. D. Beer, J. Chem. Soc., Chem. Commun., 1996, 689; (c) C. Seel and F. Vogtle, Angew. Chem., Int. Ed. Engl., 1992, 31, 528.
8. (a) C. Raposo, M. Almaraz, M. Martin, V. Weinrich, M. L. Mussons, V. Alcazar, M. C. Caballero and J. R. Morán, Chem. Lett., 1995, 37, 2795; (b) E. Fan, S. A. Van Arman, S. Kincaid and A. D. Hamilton, J. Am. Chem. Soc., 1993, 115, 369; (c) R. J. Harlow, J. Am. Chem. Soc., 1994, 116, 7072.
9. A. P. Bisson, V. M. Lynch, M.-K. C. Monahan and E. V. Anslyn, Angew. Chem., Int. Ed. Engl., 1997, 36, 2340.
10. S. Valiyaveettil, J. F. J. Engbersen, W. Verboom and D. N. Reinhoudt, Angew. Chem., Int. Ed. Engl., 1993, 32, 900.
11. S. Nishizawa, H. Kaneda, T. Uchida and N. Teramae, J. Chem. Soc., Perkin Trans. 2, 1998, 2325.
12. (a) M. E. Huston, E. U. Akkaya and A. W. Czarnik, J. Am. Chem. Soc., 1989, 111, 8735; (b) D. H. Vance and A. W. Czarnik, J. Am. Chem. Soc., 1994, 116, 9397.
13. S. Watanabe, O. Onogawa, Y. Komatsu and K. Yoshida, J. Am. Chem. Soc., 1998, 120, 229.
14. (a) S. Fery-Forgues, M. Le Bris, J. Guette and B. Valeur, J. Phys. Chem., 1988, 92, 6233; B. Valeur, J. Pouget, J. Bourson, M. Kaschke and N. P. Ernsting, J. Phys. Chem., 1992, 96, 6545; (b) J. Bourson, J. Pouget and B. Valeur, J. Phys. Chem., 1993, 97, 4552.