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Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution–solid interface

Nature Chemistry volume 8, pages 711–717 (2016)Cite this article

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Abstract

A dominant theme within the research on two-dimensional chirality is the sergeant–soldiers principle, wherein a small fraction of chiral molecules (sergeants) is used to skew the handedness of achiral molecules (soldiers) to generate a homochiral surface. Here, we have combined the sergeant–soldiers principle with temperature-dependent molecular self-assembly to unravel a peculiar chiral amplification mechanism at the solution–solid interface in which, depending on the concentration of a sergeant–soldiers solution, the majority handedness of the system can either be amplified or entirely reversed after an annealing step, furnishing a homochiral surface. Two discrete pathways that affect different stages of two-dimensional crystal growth are invoked for rationalizing this phenomenon and we present a set of experiments where the access to each pathway can be precisely controlled. These results demonstrate that a detailed understanding of subtle intermolecular and interfacial interactions can be used to induce drastic changes in the handedness of a supramolecular network.

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Figure 1: Molecular structures and models for DBA self-assembly.
Figure 2: Summary of the major chiral induction experiments carried out in this study.
Figure 3: Amplification/reversal of the initial majority (CW) handedness on annealing as a function of total concentration.
Figure 4: Enantioselective adsorption of cDBA-OC12(S).
Figure 5: Control over the sergeant–soldiers and host–guest pathways by molecular design.

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Acknowledgements

This work is supported by the Fund of Scientific Research-Flanders (FWO), KU Leuven (GOA 11/003), the Belgian Federal Science Policy Office (IAP-7/05) and JSPS KAKENHI grant nos. 10252628 and 26620063. The research leading to these results has also received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement no. 340324. H.C. is an FWO Pegasus Marie Curie Fellow.

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Authors and Affiliations

  1. Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, Leuven, B-3001, Belgium

    Yuan Fang, Elke Ghijsens, Oleksandr Ivasenko, Hai Cao, Kunal S. Mali & Steven De Feyter

  2. Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, 560-8531, Osaka, Japan

    Aya Noguchi, Kazukuni Tahara & Yoshito Tobe

  3. Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, 214-8571, Kawasaki, Japan

    Kazukuni Tahara

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  1. Yuan Fang
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Contributions

Y.F., E.G., O.I., H.C. and A.N. acquired the STM data. O.I. performed MM simulations. Y.F., E.G., O.I. and H.C. analysed the STM data. K.T. and Y.T. contributed to the synthesis of the DBA derivatives. O.I., K.S.M., K.T., Y.T and S.D.F. conceived and designed the concepts. O.I., K.S.M., K.T., Y.T. and S.D.F. co-wrote the paper. Y.F. and E.G. contributed equally. All authors contributed to the conception of experiments and discussion of the results and commented on the manuscript.

Corresponding authors

Correspondence to Oleksandr Ivasenko, Kunal S. Mali, Kazukuni Tahara, Yoshito Tobe or Steven De Feyter.

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Fang, Y., Ghijsens, E., Ivasenko, O. et al. Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution–solid interface. Nature Chem 8, 711–717 (2016). https://doi.org/10.1038/nchem.2514

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