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From helical to planar chirality by on-surface chemistry

Nature Chemistry volume 9, pages 213–218 (2017)Cite this article

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Abstract

The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic–inorganic chiral interfaces.

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Figure 1: Proposed concept of global mirror-symmetry breaking in the system of prochiral molecules on an achiral substrate.
Figure 2: The enantiopure benzo[2,1-g:3,4-g′]dichrysene (P)-DBH on Ag(111) and changes in morphology of adsorbates on annealing at 520 and 670 K.
Figure 3: Transformation products P1, P2 and P3 of the annealing of (P)-DBH on Ag(111) at 520–670 K, and elucidation of their structures, calculated models and proposed reaction mechanism.
Figure 4: Distribution of the handednesses of the adsorbed products P1 and P2 after annealing the enantiopure (P)-DBH on Ag(111) at 520 K for 5 min.
Figure 5: The occurrence of the molecular adsorbates P1, P2 and P3 and % e.e. of P1 and P2 after annealing the enantiopure (P)-DBH on Ag(111) at various temperatures.

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Acknowledgements

This work was financially supported by a Czech Science Foundation grant (14-29667S, 14-16963J) and by the Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences (RVO: 61388963).

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Authors and Affiliations

  1. Institute of Physics, Czech Academy of Sciences, Cukrovarnická 10, Prague 6, 162 00, Czech Republic

    Oleksandr Stetsovych, Martin Švec, Krzysztof Kosmider & Pavel Jelínek

  2. Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, Prague 6, 166 10, Czech Republic

    Jaroslav Vacek, Jana Vacek Chocholoušová, Andrej Jančařík, Jiří Rybáček, Irena G. Stará & Ivo Starý

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  1. Oleksandr Stetsovych
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Contributions

P.J. and I.S. conceived the project and designed the experiments. O.S. and M.Š. performed and analysed the SPM experiments. A.J. synthesized racemic DBH, and J.R. resolved the racemic DBH into enantiomers. J.V.C., J.V., K.K. and P.J. performed theoretical calculations and interpreted their results. I.S. and I.G.S. interpreted the chemical transformations. P.J., O.S., M.Š., I.S. and I.G.S. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

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Correspondence to Pavel Jelínek or Ivo Starý.

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The authors declare no competing financial interests.

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Stetsovych, O., Švec, M., Vacek, J. et al. From helical to planar chirality by on-surface chemistry. Nature Chem 9, 213–218 (2017). https://doi.org/10.1038/nchem.2662

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