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Control and induction of surface-confined homochiral porous molecular networks

Nature Chemistry volume 3, pages 714–719 (2011)Cite this article

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A Corrigendum to this article was published on 24 October 2014

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Abstract

Homochirality is essential to many biological systems, and plays a pivotal role in various technological applications. The generation of homochirality and an understanding of its mechanism from the single-molecule to supramolecular level have received much attention. Two-dimensional chirality is a subject of intense interest due to the unique possibilities and consequences of confining molecular self-assembly to surfaces or interfaces. Here, we report the perfect generation of two-dimensional homochirality of porous molecular networks at the liquid–solid interface in two different ways: (i) by self-assembly of homochiral building blocks and (ii) by self-assembly of achiral building blocks in the presence of a chiral modifier via a hierarchical structural recognition process, as revealed by scanning tunnelling microscopy. The present results provide important impetus for the development of two-dimensional crystal engineering and may afford opportunities for the utilization of chiral nanowells in chiral recognition processes, as nanoreactors and as data storage systems.

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Figure 1: 2D self-assembly of DBAs at the liquid–solid interface.
Figure 2: Self-assemblies of cDBAs at the 1-phenyloctane/graphite interface.
Figure 3: Molecular models of pairs of cDBA-OC12-(S)-OC13-(R) and heteromolecular pairs formed bycDBA-OC12-(S)-OC13-(R) and DBA-OC12.
Figure 4: Chirality induction experiments with cDBA-OC12-(S)-OC13-(R) as chiral modifier.
Figure 5: Molecular models of CCW (left) and CW (right) hexagonal structures formed from one cDBA and five achiral DBAs.

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  • 24 October 2014

    In the version of this Article originally published, a systematic error in converting the energies obtained by molecular mechanics calculations to the total energies used to evaluate the relative stabilities of the molecular network models, led to incorrect energy values being reported. The correct values are as follows: In 'Control of homochirality in a porous molecular network', modelling of hexamers of cDBA-OC12-( S) CW structure was found to be 9.66 kcal mol-1 more stable than the CCW pattern. In 'Chiral induction in a porous molecular network', the difference between CW and CCW hexamers formed by five molecules of DBA-OC12 and one of cDBA-OC12-( S) was found to be only 0.24 kcal mol−1. In 'Hierarchical chiral induction mechanism', for cyclic hexamers of one chiral cDBA-OC12-( S )-OC13-( R) and five achiral DBA-OC12 on graphite, the CW hexagonal structure is favoured by 3.88 kcal mol−1. In comparison, in similar structures made from cDBA-OC12-( S )-OC13-( R) and DBA-OC13 the energy difference between the CW and CCW structures was only 1.33 kcal mol−1. These errors do not affect the conclusions of the work, and all of the values have been corrected in the online versions of the Article.

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Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science, and Technology (Japan), the Fund of Scientific Research – Flanders (FWO), K.U.Leuven (GOA), the Belgian Federal Science Policy Office (IAP-6/27, NMP4-SL-2008-214340, project RESOLVE), and the JSPS and FWO under the Japan–Belgium Research Cooperative Program. E.G. and J.A. are grateful to the Agency for Innovation by Science and Technology in Flanders (IWT). M.O.B. acknowledges a Marie Curie Intra-European Fellowship.

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Authors and Affiliations

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

    Kazukuni Tahara, Hiroyuki Yamaga, Koji Inukai & Yoshito Tobe

  2. Department of Chemistry, Division of Molecular and Nanomaterials, Laboratory of Photochemistry and Spectroscopy, Katholieke Universiteit Leuven (KULeuven), Celestijnenlaan 200 F, Leuven, B-3001, Belgium

    Elke Ghijsens, Jinne Adisoejoso, Matthew O. Blunt & Steven De Feyter

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Contributions

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

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Correspondence to Steven De Feyter or Yoshito Tobe.

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Tahara, K., Yamaga, H., Ghijsens, E. et al. Control and induction of surface-confined homochiral porous molecular networks. Nature Chem 3, 714–719 (2011). https://doi.org/10.1038/nchem.1111

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