Article | Published:

Broken symmetry and the variation of critical properties in the phase behaviour of supramolecular rhombus tilings

Nature Chemistry volume 4, pages 112117 (2012) | Download Citation

Abstract

The tiling of surfaces has long attracted the attention of scientists, not only because it is intriguing intrinsically, but also as a way to control the properties of surfaces. However, although random tiling networks are studied increasingly, their degree of randomness (or partial order) has remained notoriously difficult to control, in common with other supramolecular systems. Here we show that the random organization of a two-dimensional supramolecular array of isophthalate tetracarboxylic acids varies with subtle chemical changes in the system. We quantify this variation using an order parameter and reveal a phase behaviour that is consistent with long-standing theoretical studies on random tiling. The balance between order and randomness is driven by small differences in intermolecular interaction energies, which can be related by numerical simulations to the experimentally measured order parameter. Significant variations occur with very small energy differences, which highlights the delicate balance between entropic and energetic effects in complex self-assembly processes.

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Acknowledgements

We thank the UK Engineering and Physical Sciences Research Council (EPSRC) for financial support under grant EP/D048761/01. J.P.G. was supported by EPSRC Grant No. GR/S54074/01. A.S. was supported by the Leverhulme Trust (ECF/2010/0380) and the EPSRC (EP/P502632/1). M.S. acknowledges receipt of a Royal Society Wolfson Merit Award and an European Research Council Advanced Grant. N.R.C. acknowledges receipt of a Royal Society Leverhulme Trust Senior Research Fellowship.

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Affiliations

  1. School of Physics and Astronomy, University of Nottingham, University Park, Nottingham NG7 2RD, UK

    • Andrew Stannard
    • , James C. Russell
    • , Matthew O. Blunt
    • , Juan P. Garrahan
    •  & Peter H. Beton
  2. School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK

    • Christos Salesiotis
    • , María del Carmen Giménez-López
    • , Nassiba Taleb
    • , Martin Schröder
    •  & Neil R. Champness

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Contributions

A.S., J.C.R., M.O.B., J.P.G., N.R.C. and P.H.B. designed and conceived the experiment, A.S., J.C.R. and M.O.B. performed the experiments, A.S. and J.P.G. performed the numerical simulations, C.S., M.C.G-L., N.T., M.S. and N.R.C. prepared the materials, A.S., J.P.G., M.O.B., J.C.R. and P.H.B. analysed the data, A.S., J.P.G. and P.H.B. co-wrote the paper and all authors provided revisions and comments on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Andrew Stannard or Peter H. Beton.

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DOI

https://doi.org/10.1038/nchem.1199

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