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Chiral self-sorting and amplification in isotropic liquids of achiral molecules

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Abstract

According to our present knowledge, the spontaneous resolution of racemic mixtures of chiral molecules or chiral conformers of achiral molecules into macroscopic chiral superstructures requires the confinement of these molecules in a crystal lattice, on surfaces or in other well-ordered assemblies. Herein we provide the first experimental evidence that mirror-symmetry breaking can also take place at a liquid–liquid phase transition in isotropic liquids of achiral molecules, even at relatively high temperatures around 200 °C. It is proposed that cooperative segregation of enantiomorphic molecular conformations gives rise to a conglomerate of two chiral and immiscible liquids. In these liquid conglomerates a strong chiral amplification was observed, which led to degeneracy from a stochastic distribution and eventually provided uniform chirality. We anticipate that this work will contribute to the understanding of symmetry breaking in soft matter and provide a new tool for the identification of chirality traces, and possibly affect the discussion of the emergence of chirality in prebiotic systems.

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Figure 1: Structure and phase transitions of compound 1a.
Figure 2: Photomicrographs of the Iso1[*] phase of 1a.
Figure 3: XRD patterns, molecular conformations and self-assembly of compound 1a.
Figure 4: Change of cluster size at the Iso2–Iso1[*] transition.
Figure 5: Other compounds with Iso1–Iso2 phase transitions.
Figure 6: Mixtures of 1a with an n-alkane.

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Acknowledgements

M.P. and C.T. acknowledge the support of the German Research Foundation (DFG, FG 1145, TS 39/21-2). We thank A. Achilles and K. Saalwächter, Institute of Physics, University Halle, for discussions and NMR studies.

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Authors and Affiliations

  1. Institute of Chemistry, Organic Chemistry, Martin-Luther University Halle-Wittenberg, Halle/Saale, D-06120, Germany

    Christian Dressel, Tino Reppe, Marko Prehm, Marcel Brautzsch & Carsten Tschierske

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  1. Christian Dressel
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Contributions

The compound was designed by C.D. and C.T. and synthesized and purified by T.R. and C.D. Optical experiments were conducted by C.D. and XRD investigations by M.P. The manuscript was written by C.T. and computations were performed by M.B. All authors discussed the results and commented on the manuscript.

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Correspondence to Carsten Tschierske.

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Dressel, C., Reppe, T., Prehm, M. et al. Chiral self-sorting and amplification in isotropic liquids of achiral molecules. Nature Chem 6, 971–977 (2014). https://doi.org/10.1038/nchem.2039

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