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Exceptionally large positive and negative anisotropic thermal expansion of an organic crystalline material

Nature Materials volume 9, pages 3639 (2010) | Download Citation

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Abstract

In general, the relatively modest expansion experienced by most materials on heating is caused by increasing anharmonic vibrational amplitudes of the constituent atoms, ions or molecules1. This phenomenon is called positive thermal expansion (PTE) and usually occurs along all three crystallographic axes. In very rare cases, structural peculiarities may give rise either to anomalously large PTE, or to negative thermal expansion (NTE, when lattice dimensions shrink with heating)2,3,4. As NTE and unusually large PTE are extremely uncommon for molecular solids, mechanisms that might give rise to such phenomena are poorly understood. Here we show that the packing arrangement of a simple dumbbell-shaped organic molecule, coupled with its intermolecular interactions, facilitates a cooperative mechanical response of the three-dimensional framework to changes in temperature. A series of detailed structural determinations at 15-K intervals has allowed us to visualize the process at the molecular level. The underlying mechanism is reminiscent of a three-dimensional (3D) folding trellis and results in exceptionally large and reversible uniaxial PTE and biaxial NTE of the crystal. Understanding such mechanisms is highly desirable for the future design of sensitive thermomechanical actuators.

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References

  1. 1.

    & Solid State Physics (Holt, Rinehart & Winston, 1976).

  2. 2.

    et al. Colossal positive and negative thermal expansion in the framework material Ag3[Co(CN)6]. Science 319, 794–797 (2008).

  3. 3.

    , , & Negative thermal expansion. J. Phys. Condens. Matter 17, R217–R252 (2005).

  4. 4.

    , & Impact of metallophilicity on ‘colossal’ positive and negative thermal expansion in a series of isostructural dicyanometallate coordination polymers. J. Am. Chem. Soc. 131, 4866–4871 (2009).

  5. 5.

    , , & Crystalline molecular machines: A quest toward solid-state dynamics and function. Acc. Chem. Res. 39, 413–422 (2006).

  6. 6.

    Negative thermal expansion materials. J. Chem. Soc. Dalton. Trans. 3317–3326 (1999).

  7. 7.

    , , , & The widespread occurrence of negative thermal expansion in zeolites. J. Mater. Chem. 11, 212–216 (2001).

  8. 8.

    & Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials. Phys. Rev. B 71, 140301–140304 (2005).

  9. 9.

    , & Guest-dependent negative thermal expansion in nanoporous Prussian blue analogues MIIPtIV(CN)6·x{H2O} (0≤x≤2; M=Zn, Cd). J. Am. Chem. Soc. 127, 17980–17981 (2005).

  10. 10.

    et al. Negative thermal expansion in the metal–organic framework material Cu3(1,3,5−benzenetricarboxylate)2. Angew. Chem. Int. Ed. 47, 8929–8932 (2008).

  11. 11.

    , , , & Origin of the exceptional negative thermal expansion in metal–organic framework-5 Zn4O(1,4−benzenedicarboxylate)3. Phys. Rev. B 78, 054114 (2008).

  12. 12.

    & Thermal expansion and Grüneisen parameters of isotropic and oriented polyethylene. J. Polym. Sci. Polym. Phys. Ed. 22, 835–846 (1984).

  13. 13.

    , & Observation of uniaxial negative thermal expansion in an organic crystal. Angew. Chem. Int. Ed. 41, 754–756 (2002).

  14. 14.

    et al. Large uniaxial negative thermal expansion in pentacene due to steric hindrance. Phys. Rev. B 76, 205203 (2007).

  15. 15.

    , & Thermal Expansion of Crystals (Pergamon, 1979).

  16. 16.

    et al. Solid-state self-inclusion: The missing link. Angew. Chem. Int. Ed. 45, 5354–5358 (2006).

  17. 17.

    , & Crystallographic observation of dynamic gas adsorption sites and thermal expansion in a breathable fluorous metal–organic framework. Angew. Chem. Int. Ed. 48, 2500–2505 (2009).

  18. 18.

    , & Towards quantitative analysis of intermolecular interactions with Hirshfeld surfaces. Chem. Commun. 3814–3816 (2007).

  19. 19.

    & The thermal expansion of graphite from 15 C to 800 C: Part I. Experimental. Proc. Phys. Soc. Lond. 57, 477–486 (1945).

  20. 20.

    , , , & Temperature-induced valence transition and associated lattice collapse in samarium fulleride. Nature 425, 599–602 (2003).

  21. 21.

    , , & Zero thermal expansion in YbGaGe due to an electronic valence transition. Nature 425, 702–705 (2003).

  22. 22.

    , , & Novel thermal expansion of lead titanate. Rare Metals 22, 294–297 (2003).

  23. 23.

    , & Origin of the invar effect in iron-nickel alloys. Nature 400, 46–49 (1999).

  24. 24.

    & Crystal vibrations and intermolecular forces of polymethylene crystals. J. Chem. Phys. 43, 1245–1258 (1965).

  25. 25.

    Crystal from first principles. Nature 335, 201 (1988).

  26. 26.

    Are crystal structures predictable? Chem. Commun. 545–548 (2003).

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Acknowledgements

We are grateful to A. Pietraszko of the Institute of Low Temperature and Structure Research of the Polish Academy of Sciences in Wrocław for the X-ray powder diffraction studies. We thank the National Research Foundation and Department of Science and Technology (SARCHI Program) for support of this work. Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre under reference numbers CCDC 723,906–723,913. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK).

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Affiliations

  1. Department of Chemistry and Polymer Science, University of Stellenbosch, Stellenbosch 7600, South Africa

    • Dinabandhu Das
    • , Tia Jacobs
    •  & Leonard J. Barbour

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Contributions

T.J. synthesized the compound and carried out the initial crystal-structure determinations and thermal analyses. D.D. carried out the variable-temperature studies and wrote the initial draft of the letter. L.J.B. wrote the final draft, prepared the figures and coordinated the project.

Corresponding author

Correspondence to Leonard J. Barbour.

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DOI

https://doi.org/10.1038/nmat2583

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