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Ion-triggered spring-like motion of a double helicate accompanied by anisotropic twisting

Nature Chemistry volume 2, pages 444–449 (2010)Cite this article

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Abstract

Molecules that extend and contract under external stimuli are used to build molecular machines with nanomechanical functions. But although common in biological systems, such extension and contraction motions with helical molecules have rarely been accompanied by unidirectional twisting in synthetic systems. Here we show that sodium ions can trigger the reversible anisotropic twisting of an enantiomeric double-stranded helicate, without racemization. An optically active helicate consisting of two tetraphenol strands bridged by two spiroborate groups sandwiches a sodium ion. On removal of the central sodium—through addition of a cryptand [2.2.1] in solution—the double helicate extends. Crystallographic and nuclear magnetic resonance studies reveal that the extended helicate is over twice as long as the initial molecule, and is twisted in the right-handed direction. Circular dichroism analysis suggests that the twisting doesn't affect the helicate's handedness. This anisotropic extension–contraction process is reversibly triggered by the successive addition and removal of sodium ions in solution.

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Figure 1: Synthesis and optical resolution.
Figure 2: Capped-stick representations of the crystal structures of the trinuclear boron helicates.
Figure 3: Synthesis and characterization of the dinuclear helicate.
Figure 4: Anisotropic twisting motion of the helicate.

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Acknowledgements

This work was supported in part by Grant-in-Aids for Scientific Research from the Japan Society for the Promotion of Science (JSPS) and for Scientific Research on Innovative Areas, “Emergence in Chemistry” (21111508) from the MEXT. We acknowledge Y. Kondo and K. Nagamori of JASCO for their help in the measurements of the stopped-flow CD spectra.

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Authors and Affiliations

  1. Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, 464-8603, Nagoya, Japan

    Kazuhiro Miwa, Yoshio Furusho & Eiji Yashima

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  1. Kazuhiro Miwa
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  2. Yoshio Furusho
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  3. Eiji Yashima
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Contributions

Y.F. and E.Y. designed and directed the project and K.M. performed the experiments. K.M., Y.F. and E.Y. analysed and discussed the results and co-wrote the manuscript.

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Correspondence to Yoshio Furusho or Eiji Yashima.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 4287 kb)

Supplementary information

Crystallographic information for the double helicate DH2BB2−. (CIF 67 kb)

Supplementary information

Crystallographic information for the Na-containing double helicate DH2BNaB−. (CIF 71 kb)

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Miwa, K., Furusho, Y. & Yashima, E. Ion-triggered spring-like motion of a double helicate accompanied by anisotropic twisting. Nature Chem 2, 444–449 (2010). https://doi.org/10.1038/nchem.649

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