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Real-time molecular scale observation of crystal formation

Nature Chemistry volume 9, pages 369–373 (2017)Cite this article

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Abstract

How molecules in solution form crystal nuclei, which then grow into large crystals, is a poorly understood phenomenon. The classical mechanism of homogeneous crystal nucleation proceeds via the spontaneous random aggregation of species from liquid or solution. However, a non-classical mechanism suggests the formation of an amorphous dense phase that reorders to form stable crystal nuclei. So far it has remained an experimental challenge to observe the formation of crystal nuclei from five to thirty molecules. Here, using polyoxometallates, we show that the formation of small crystal nuclei is observable by cryogenic transmission electron microscopy. We observe both classical and non-classical nucleation processes, depending on the identity of the cation present. The experiments verify theoretical studies that suggest non-classical nucleation is the lower of the two energy pathways. The arrangement in just a seven-molecule proto-crystal matches the order found by X-ray diffraction of a single bulk crystal, which demonstrates that the same structure was formed in each case.

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Figure 1: Time series of MnPFOM aggregation with NaCl.
Figure 2: Correlation between cryo-TEM images and the crystal structure.
Figure 3: MD calculations for the system with NaCl.
Figure 4: Time series of MnPFOM aggregation with CsCl.

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Acknowledgements

The research at the Weizmann Institute of Science was funded by the Israel Science Foundation grant no. 763/14 and electron microscopy experiments were partially funded by Irving and Cherna Moscowitz Center for Nano and Bio-Nano Imaging of the Weizmann Institute of Science. R.N. is the Rebecca and Israel Sieff Professor of Chemistry. Research at Universitat Rovira i Virgili was supported by the Spanish Ministry of Science and Innovation (grant CTQ2014-52774-P) and the Generalitat de Catalunya (2014SGR199 and XRQTC). J.M.P. thanks the ICREA (Catalan Institution for Research and Advanced Studies) Foundation for an ICREA Academia award.

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Authors and Affiliations

  1. Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel

    Roy E. Schreiber & Ronny Neumann

  2. Department for Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel

    Lothar Houben, Sharon G. Wolf & Gregory Leitus

  3. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, Tarragona, 43007, Spain

    Zhong-Ling Lang, Jorge J. Carbó & Josep M. Poblet

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Contributions

R.E.S. carried out the majority of the research, R.E.S., L.H. and S.G.W. carried out the electron microscopy measurements and analysed tomography data, G.L. carried out the X-ray diffraction measurements, Z.-l.L., J.J.C. and J.M.P. did the molecular dynamics calculations and R.N. supervised the research.

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Correspondence to Ronny Neumann.

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Supplementary information

Supplementary information

Supplementary information (PDF 2363 kb)

Supplementary information

Crystallographic data for compound Na2K6-MnPFOM. (CIF 735 kb)

Supplementary information

Crystallographic data for compound Cs5.5K2.5-MnPFOM. (CIF 892 kb)

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Schreiber, R., Houben, L., Wolf, S. et al. Real-time molecular scale observation of crystal formation. Nature Chem 9, 369–373 (2017). https://doi.org/10.1038/nchem.2675

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