Giant negative linear compressibility in zinc dicyanoaurate

Abstract

The counterintuitive phenomenon of negative linear compressibility (NLC) is a highly desirable but rare property exploitable in the development of artificial muscles1, actuators2 and next-generation pressure sensors3. In all cases, material performance is directly related to the magnitude of intrinsic NLC response. Here we show the molecular framework material zinc(II) dicyanoaurate(I), Zn[Au(CN)2]2, exhibits the most extreme and persistent NLC behaviour yet reported: under increasing hydrostatic pressure its crystal structure expands in one direction at a rate that is an order of magnitude greater than both the typical contraction observed for common engineering materials4 and also the anomalous expansion in established NLC candidates3. This extreme behaviour arises from the honeycomb-like structure of Zn[Au(CN)2]2 coupling volume reduction to uniaxial expansion5, and helical Au…Au ‘aurophilic’ interactions6 accommodating abnormally large linear strains by functioning as supramolecular springs.

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Figure 1: The β-quartz-like framework structure of Zn[Au(CN)2]2 functions as a ‘molecular honeycomb’ to give giant negative linear compressibility.
Figure 2: The compressibility of Zn[Au(CN)2]2 is quantified by the variation in crystallographic unit-cell parameters.
Figure 3: Compressibility enhancement in Zn[Au(CN)2]2 via ‘spring’-like deformations.
Figure 4: Relationship between the ambient (I) and high-pressure (II) phases of Zn[Au(CN)2]2.

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Acknowledgements

A.B.C. and A.L.G. acknowledge financial support from the EPSRC (EP/G004528/2) and the ERC (Grant Ref: 279705), and are grateful to R. I. Cooper and P. J. Saines (Oxford) for assistance. J.H. thanks H. Shepherd, G. Molnar (LCC, Toulouse), D. Maurin (L2C), D. Bourgogne (ICGM), S. Klotz (IMPMC, Paris), K. Murato (Osaka) and D. Granier (ICGM) for technical assistance, and the ANR for financial support (Contract ANR-09-BLAN-0018-01).

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A.B.C., J.H. and A.L.G. conceived the study; A.B.C. made the sample; A.B.C., J.C., C.L., J.R., A.v.d.L., A.L.T, V.D., J.H. and A.L.G. performed the experiments; A.B.C., L.P., J.H. and A.L.G. analysed and interpreted the data; A.B.C. and A.L.G. wrote the paper.

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Correspondence to Andrew L. Goodwin.

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The authors declare no competing financial interests.

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Cairns, A., Catafesta, J., Levelut, C. et al. Giant negative linear compressibility in zinc dicyanoaurate. Nature Mater 12, 212–216 (2013). https://doi.org/10.1038/nmat3551

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