Abstract
FOR over 50 years urea inclusion compounds (UICs)-in which molecules are entrapped within the cavities of a hydrogen-bonded urea network—have intrigued chemists, crystallographers and spectroscopists1. Most previous work on these and other inclusion compounds has focused on intrachannel interactions and dynamics. We have now found that UICs can serve as useful models to probe long-range interactions and cooperative phenomena in crystals. Here we report the structure of 2,10-undecanedione/urea (1:9) (1/ urea), in which an extended hydrogen-bonded array connecting hosts and guests serves to distort the urea channel away from the hexagonal symmetry normally observed for UIC crystals. The distortion is large enough, and exhibits enough cooperativity, to generate macroscopic domains, but is small enough to allow facile domain reorientation under small compressive stresses. By incorporating a specific impurity (2-undecanone) into 1/urea, we can modify the domain size and optical properties, and make the domain reorientation spontaneously reversible when the uniaxial stress is released. All of these phenomena can be understood in terms of cooperative interactions between different channels of the hydrogen-bonded network formed by urea and its guest.
Similar content being viewed by others
References
Takemoto, K. & Sonoda, N. in Inclusion Compounds Vol. II (eds Atwood, J. L., Davies, J. E. D. & MacNicol, D. D.) 47–67 (Academic, London, 1984).
Smith, A. E. Acta crystallogr. 5, 224–235 (1952).
Harris, K. D. M. & Thomas, J. M. J. chem. Soc., Faraday Trans. 86, 2985–2996 (1990).
Hollingsworth, M. D., Santarsiero, B. D. & Harris, K. D. M. Angew. Chem. int. Edn engl. 33, 649–652 (1994).
Hollingsworth, M. D., Brown, M. E., Santarsiero, B. D., Huffman, J. C. & Goss, C. R. Chem. Mater. 6, 1227–1244 (1994).
Otto, J. Acta crystallogr. B28, 543–551 (1972).
Greenfield, M. S., Vold, R. L. & Vold, R. R. J. chem. Phys. 83, 1440–1443 (1985).
Greenfield, M. S., Vold, R. L. & Vold, R. R. Molec. Phys. 66, 269–298 (1989).
Guillaume, F., Smart, S. P., Harris, K. D. M. & Dianoux, A. J. J. Phys.: Condens. Matter 6, 2169–2184 (1994).
Schmicker, D., van Smaalen, S., de Boer, J. L., Haas, C. & Harris, K. D. M. Phys. Rev. Lett 74, 734–737 (1995).
Harris, K. D. M. J. Solid St. Chem. 106, 83–98 (1993).
Lenné, H. U., Mez, H. C. & Schlenk, W. Jr Justus Liebigs Annln Chem. 732, 70–96 (1970).
Rennie, A. J. O. & Harris, K. D. M. J. Chem. Phys. 96, 7117–7124 (1992).
Hollingsworth, M. D. & Goss, C. R. Molec. Cryst. liq. Cryst. 219, 43–62 (1992).
Abrahams, S. C. Mater. Res. Bull. 6, 881–890 (1971).
Saljé, E. K. H. Phase Transitions in Ferroelastic and Co-elastic Crystals (Cambridge Univ. Press, 1990).
Callister, W. D. Jr Materials Science and Engineering: an introduction (Wiley, New York, 1994).
Bornarel, J., Lajzerowicz, J. & Legrand, J. F. Ferroelectrics 7, 313–314 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Brown, M., Hollingsworth, M. Stress-induced domain reorientation in urea inclusion compounds. Nature 376, 323–327 (1995). https://doi.org/10.1038/376323a0
Issue Date:
DOI: https://doi.org/10.1038/376323a0
- Springer Nature Limited
This article is cited by
-
Compressed alkanes in reversible encapsulation complexes
Nature Chemistry (2009)
-
Molecular and supramolecular structure of 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane, tetrahydrofuran solvate
Journal of Chemical Crystallography (1997)