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Encoding complexity within supramolecular analogues of frustrated magnets

Nature Chemistry volume 8, pages 442–447 (2016)Cite this article

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Abstract

The solid phases of gold(I) and/or silver(I) cyanides are supramolecular assemblies of inorganic polymer chains in which the key structural degrees of freedom—namely, the relative vertical shifts of neighbouring chains—are mathematically equivalent to the phase angles of rotating planar (‘XY’) spins. Here, we show how the supramolecular interactions between chains can be tuned to mimic different magnetic interactions. In this way, the structures of gold(I) and/or silver(I) cyanides reflect the phase behaviour of triangular XY magnets. Complex magnetic states predicted for this family of magnets—including collective spin-vortices of relevance to data storage applications—are realized in the structural chemistry of these cyanide polymers. Our results demonstrate how chemically simple inorganic materials can behave as structural analogues of otherwise inaccessible ‘toy’ spin models and also how the theoretical understanding of those models allows control over collective (‘emergent’) phenomena in supramolecular systems.

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Figure 1: Crystal structures of AuCN and AgCN and their relationship to the ground states of triangular XY (anti)ferromagnets.
Figure 2: Interactions in AuCN and AgCN.
Figure 3: Interactions and structural complexity in Au1/2Ag1/2(CN).

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Acknowledgements

A.B.C., M.J.C., J.A.M.P. and A.L.G. acknowledge financial support from the Engineering and Physical Sciences Research Council (EPSRC; EP/G004528/2), the Science and Technology Facilities Council (STFC) and the European Research Council (ERC; grant ref: 279705). High-pressure synchrotron X-ray powder diffraction measurements were carried out at the I15 Beamline, Diamond Light Source, UK. Quantum chemistry calculations made use of high performance computing resources from GENCI (grant x2015087069).

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Authors and Affiliations

  1. Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK

    Andrew B. Cairns, Matthew J. Cliffe, Joseph A. M. Paddison & Andrew L. Goodwin

  2. European Synchrotron Radiation Facility, 71 avenue des Martyrs, Grenoble, 38043, France

    Andrew B. Cairns

  3. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK

    Matthew J. Cliffe

  4. ISIS Facility, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, OX11 0QX, UK

    Joseph A. M. Paddison & Matthew G. Tucker

  5. School of Physics, Georgia Institute of Technology, 837 State Street, Atlanta, 30332, Georgia, USA

    Joseph A. M. Paddison

  6. Diamond Light Source, Chilton, OX11 0DE, UK

    Dominik Daisenberger & Matthew G. Tucker

  7. PSL Research University, Chimie ParisTech – CNRS, Institut de Recherche de Chimie Paris, Paris, 75005, France

    François-Xavier Coudert

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Contributions

A.B.C., M.J.C., J.A.M.P., F.-X.C. and A.L.G. conceived and designed the study. A.B.C., D.D. and M.G.T. performed the experiments. A.B.C., M.J.C., J.A.M.P. and A.L.G. interpreted the experimental data. F.-X.C. performed and interpreted the quantum chemistry calculations. A.L.G. wrote the paper. All authors discussed and commented on the manuscript.

Corresponding authors

Correspondence to François-Xavier Coudert or Andrew L. Goodwin.

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The authors declare no competing financial interests.

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Cairns, A., Cliffe, M., Paddison, J. et al. Encoding complexity within supramolecular analogues of frustrated magnets. Nature Chem 8, 442–447 (2016). https://doi.org/10.1038/nchem.2462

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