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Atomically precise inorganic helices with a programmable irrational twist

Nature Materials (2024)Cite this article

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Abstract

Helicity in solids often arises from the precise ordering of cooperative intra- and intermolecular interactions unique to natural, organic or molecular systems. This exclusivity limited the realization of helicity and its ensuing properties in dense inorganic solids. Here we report that Ga atoms in GaSeI, a representative III–VI–VII one-dimensional (1D) van der Waals crystal, manifest the rare Boerdijk–Coxeter helix motif. This motif is a non-repeating geometric pattern characterized by 1D face-sharing tetrahedra whose adjacent vertices are rotated by an irrational angle. Using InSeI and GaSeI, we show that the modularity of 1D van der Waals lattices accommodates the systematic twisting of a periodic tetrahelix with a 41 screw axis in InSeI to an infinitely extending Boerdijk–Coxeter helix in GaSeI. GaSeI crystals are non-centrosymmetric, optically active and exfoliable to a single chain. These results present a materials platform towards understanding the origin and physical manifestation of aperiodic helicity in low-dimensional solids.

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Fig. 1: Helices possessing rational and irrational twist angles.
Fig. 2: Synthesis and single-crystal structure of GaSeI.
Fig. 3: Microstructure and nanoscale morphology of unbundled GaSI crystals.
Fig. 4: Hallmarks of the B-C helix geometry and signatures of B-C helicity in GaSeI.
Fig. 5: B-C helix parameters and origin of B-C helicity in GaSeI.
Fig. 6: Optical spectroscopy of GaSeI microcrystallites.

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Data availability

Crystallographic data can be obtained free of charge from the Cambridge Crystallographic Data Centre (CCDC) via www.ccdc.cam.ac.uk/data_request/cif (CCDC deposition no. 2360595). All other data supporting the findings of this study are available within the Article and its Supplementary Information. Any additional material is available from the corresponding author upon reasonable request.

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Acknowledgements

We thank the UC Irvine Department of Chemistry X-ray crystallography facility for the instrumental support on the single-crystal diffraction experiments. T.A.K. and J.Z. acknowledge the UC Irvine School of Physical Sciences and Department of Chemistry for funding. We also thank the UC Irvine Laser Spectroscopy Labs. D.A.F. acknowledges support through NIH GM R21-GM141774. Several aspects of this work were performed at the UC Irvine Materials Research Institute (IMRI). Facilities and instrumentation at IMRI are supported, in part, by the National Science Foundation through the UC Irvine Materials Research Science and Engineering Center grant number DMR-2011967. XPS was performed using instrumentation funded in part by the National Science Foundation Major Research Instrumentation Program under grant number CHE-1338173. AFM was performed using an Anton Paar Tosca 400 AFM on loan to IMRI from Anton Paar GmbH.

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  1. These authors contributed equally: Dmitri Leo Mesoza Cordova, Kenneth Chua.

Authors and Affiliations

  1. Department of Chemistry, University of California Irvine, Irvine, CA, USA

    Dmitri Leo Mesoza Cordova, Kenneth Chua, Tyler A. Kerr, David Knez, Diana Lopez, Joseph Ziller, Dmitry A. Fishman & Maxx Q. Arguilla

  2. Irvine Materials Research Institute, University of California Irvine, Irvine, CA, USA

    Toshihiro Aoki

  3. Department of Chemistry, Princeton University, Princeton, NJ, USA

    Grigorii Skorupskii

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Contributions

Conceptualization: M.Q.A. Methodology: D.L.M.C., K.C., G.S., D.A.F. and M.Q.A. Investigation: D.L.M.C., K.C., T.A.K., T.A., D.K., D.L. and D.A.F. Visualization: D.L.M.C., K.C., D.A.F. and M.Q.A. Funding acquisition: M.Q.A. Project administration: M.Q.A. Supervision: M.Q.A. Writing—original draft: D.L.M.C., K.C. and M.Q.A. Writing—review and editing: D.L.M.C., K.C., T.A.K., T.A., D.K., G.S., D.L., J.Z., D.A.F. and M.Q.A.

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Correspondence to Maxx Q. Arguilla.

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Cordova, D.L.M., Chua, K., Kerr, T.A. et al. Atomically precise inorganic helices with a programmable irrational twist. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01963-4

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