Abstract
THE encapsulation of molecules within larger molecular or supramolecular cages (see ref. 1 for examples) brings about many interesting phenomena, among them the stabilization of reactive intermediates2, new forms of stereoisomerism3, and templating of the cage itself4,5. Here we describe a self-assembling hydrogen-bonded molecular capsule that encapsulates guest molecules in a reversible, apparently entropy-driven process, giving rise to unusual temperature dependence of the formation process. The positive entropy of formation—at first sight unexpected—seems to be the result of the fact that more than one solvent molecule is included in the 'bare' cage, making their replacement by a single large molecule (here adamantane or ferrocene) entropically favourable.
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References
Cram, D. J. Nature 356, 29–36 (1992).
Cram, D. J. & Tanner, M. E. Angew. Chem. (int. edn Engl.) 30, 1024–1027 (1991).
Timmerman, P. et al. Angew. Chem. (int. edn Engl.) 33, 2345–2348 (1994).
Chapman, R. G. & Sherman, J. C. J. Am. chem. Soc. 117, 9081–9082 (1995).
Chapman, R. G., Chopra, N., Cochien, E. D. & Sherman, J. C. J. Am. chem. Soc. 116, 369–370 (1994).
Meissner, R. S., Rebek, J. Jr & Mendoza, J. D. Science 270, 1485–1488 (1995).
Lindsey, J. S. New J. Chem. 15, 153–180 (1991).
Dunitz, J. D. Chem. Biol. 2, 709–712 (1995).
Peterson, B. R., Wallimann, P., Carcanague, D. R. & Diederich, F. Tetrahedron 51, 401–421 (1995).
Searle, M. S., Westwell, M. S. & Williams, D. H. J. chem. Soc. Perkin Trans. 2, 141–151 (1995).
Canceill, J. et al. Angew. Chem. (int. edn Engl.) 28, 1246–1248 (1989).
Cram, D. J., Choi, H.-J., Bryant, J. A. & Knobler, C. B. J. Am. chem. Soc. 114, 7748–7765 (1992).
Cram, D. J., Blanda, M. T., Paek, K. & Knobler, C. B. J. Am. chem. Soc. 114, 7765–7773 (1992).
Shimizu, K. D. & Rebek, J. Jr Proc. natn. Acad. Sci. U.S.A. 92, 12403–12407 (1995).
Mock, W. L., Irra, T. A., Wepsiec, J. P. & Adhya, M. J. org. Chem. 54, 5302–5308 (1989).
Walter, C. J., Anderson, H. L. & Sanders, J. K. M. J. chem. Soc. chem. Commun. 458–460 (1993).
Mohamadi, F. et al. J. Comput. Chem. 11, 440–467 (1990).
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Kang, J., Rebek, J. Entropically driven binding in a self-assembling molecular capsule. Nature 382, 239–241 (1996). https://doi.org/10.1038/382239a0
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DOI: https://doi.org/10.1038/382239a0
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