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Heterogeneous nucleation of organic crystals mediated by single-molecule templates

Abstract

Fundamental understanding of how crystals of organic molecules nucleate on a surface remains limited1,2,3 because of the difficulty of probing rare events at the molecular scale. Here we show that single-molecule templates on the surface of carbon nanohorns can nucleate the crystallization of two organic compounds from a supersaturated solution by mediating the formation of disordered and mobile molecular nanoclusters on the templates. Single-molecule real-time transmission electron microscopy indicates that each nanocluster consists of a maximum of approximately 15 molecules, that there are fewer nanoclusters than crystals in solution, and that in the absence of templates physisorption, but not crystal formation, occurs. Our findings suggest that template-induced heterogeneous nucleation mechanistically resembles two-step homogeneous nucleation4,5,6,7.

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Figure 1: Y′–CNH-driven crystallization of 1,3,5-tris(4-bromophenyl) benzene (Y).
Figure 2: SMRT-TEM images of Y′–CNH and precursor clusters of Y taken from the Supplementary Movies together with a molecular model of a plausible structure of clusters and its TEM simulation.
Figure 3: Size of needle crystals and clusters of Y on Y′–CNH.
Figure 4: Nucleation on a reactive surface.

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Acknowledgements

This work was partly supported by KAKENHI on Specially Promoted Research (22000008) to E.N. and Innovative Areas ‘Coordination Programming’ (Area 2107, 24108710) to K.H. from MEXT, Japan. T.H. thanks the Japan Society for Promotion of Science for a predoctoral fellowship. The CNH particles for the synthesis of amino–CNH were provided by M. Yudasaka.

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Authors

Contributions

E.N. conceived the study and co-wrote the paper with K.H. T.H. and K.H. performed the macro- and microscopic experiments and L.L. conceived the macroscopic experiments. M.K. and Y.N. performed the SMRT-TEM imaging, and interpreted the data with K.S., K.H., E.N. and T.H. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Eiichi Nakamura.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 2253 kb)

Supplementary Information

Supplementary Movie S1 (MOV 204 kb)

Supplementary Information

Supplementary Movie S2 (MOV 467 kb)

Supplementary Information

Supplementary Movie S3 (MOV 66 kb)

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Supplementary Movie S4 (MOV 535 kb)

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Supplementary Movie S5 (MOV 655 kb)

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Supplementary Movie S6 (MOV 183 kb)

Supplementary Information

Supplementary Movie S7 (MOV 3704 kb)

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Harano, K., Homma, T., Niimi, Y. et al. Heterogeneous nucleation of organic crystals mediated by single-molecule templates. Nature Mater 11, 877–881 (2012). https://doi.org/10.1038/nmat3408

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