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

Nature Materials volume 9, pages 36–39 (2010)Cite this article

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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Figure 1: Molecular structure and stacking.
Figure 2: A perspective view along [100] showing that the entire structure consists of a single 3D network of helical hydrogen-bonded chains.
Figure 3: Photomicrographs, recorded at 323 and 245 K, of the same crystal immersed in a temperature-controlled stream of dry nitrogen gas.
Figure 4: The effect of temperature on structural parameters.

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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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  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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  1. Dinabandhu Das
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  2. Tia Jacobs
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  3. 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.

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Correspondence to Leonard J. Barbour.

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Das, D., Jacobs, T. & Barbour, L. Exceptionally large positive and negative anisotropic thermal expansion of an organic crystalline material. Nature Mater 9, 36–39 (2010). https://doi.org/10.1038/nmat2583

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