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Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs

Nature Chemistry volume 8, pages 270–275 (2016)Cite this article

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Abstract

The mechanical flexibility of coordination frameworks can lead to a range of highly anomalous structural behaviours. Here, we demonstrate the extreme compressibility of the LnFe(CN)6 frameworks (Ln = Ho, Lu or Y), which reversibly compress by 20% in volume under the relatively low pressure of 1 GPa, one of the largest known pressure responses for any crystalline material. We delineate in detail the mechanism for this high compressibility, where the LnN6 units act like torsion springs synchronized by rigid Fe(CN)6 units performing the role of gears. The materials also show significant negative linear compressibility via a cam-like effect. The torsional mechanism is fundamentally distinct from the deformation mechanisms prevalent in other flexible solids and relies on competition between locally unstable metal coordination geometries and the constraints of the framework connectivity, a discovery that has implications for the strategic design of new materials with exceptional mechanical properties.

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Figure 1: Structure and pressure-induced behaviour of LnFe(CN)6 frameworks.
Figure 2: Spring-and-gear mechanism for compression.
Figure 3: Energetic origin of the behaviour.

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Acknowledgements

C.J.K. acknowledges financial support from the Australian Research Council. The neutron scattering experiments were performed under OPAL proposal P2455. The authors thank the Bragg Institute sample environment team for their assistance.

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Authors and Affiliations

  1. School of Chemistry, The University of Sydney, Sydney, 2006, New South Wales, Australia

    Samuel G. Duyker & Cameron J. Kepert

  2. Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, 2232, New South Wales, Australia

    Samuel G. Duyker, Vanessa K. Peterson, Gordon J. Kearley & Andrew J. Studer

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  1. Samuel G. Duyker
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Contributions

S.G.D., V.K.P. and C.J.K. conceived the study, analysed and interpreted the data, and wrote the paper. S.G.D., V.K.P., G.J.K. and A.J.S. performed the experiments and DFT calculations.

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Correspondence to Vanessa K. Peterson or Cameron J. Kepert.

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Duyker, S., Peterson, V., Kearley, G. et al. Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs. Nature Chem 8, 270–275 (2016). https://doi.org/10.1038/nchem.2431

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