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Mechanically interlocked daisy-chain-like structures as multidimensional molecular muscles

Nature Chemistry volume 9, pages 128–134 (2017)Cite this article

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Abstract

Daisy chains (DCs) are garlands of flowers that can be worn as bracelets and necklaces. As a result of their beautiful interlocked structures and possible muscle-like motions, cyclic molecular DCs ([cn]DCs, where n is the number of repeating units) have long been attractive synthetic targets for supramolecular chemists. Herein we report artificial molecular muscles that—unlike one-dimensional (1D) biological muscles—contract and stretch in 2D or 3D. These systems have the structures of [c3]- and [c4]DCs with subcomponents that operate as molecular switches, powered through the addition or removal of Zn2+ ions to impart muscle-like behaviour. We assembled these [c3]- and [c4]DCs selectively by exploiting structural rigidity, coordination geometries and bond rotational barriers that disfavoured the formation of smaller homologues. The switching phenomena of our [c3]- and [c4]DCs resulted in the contracted molecular muscles stretching by approximately 23 and 36%, respectively, comparable to the value (27%) for linear biological muscles.

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Figure 1: DCs and their potential switching motions.
Figure 2: Chemical structures of the hermaphroditic monomers, and the unfavourable perpendicular torsional alignment required for the bipyridine–pyridine linkages in monomer 1 to assemble into a [c3]DC.
Figure 3: The switching operation of interlocked [c4]- and [c3]DCs revealed spectroscopically.
Figure 4: Syntheses of interlocked DCs.
Figure 5: Solid-state structures of cyclic DCs
Figure 6: Selectivity in assembling cyclic DCs from different monomers, and the different sizes of the two switching states of [c3]- and [c4]DCs.

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Acknowledgements

This study was supported by the Ministry of Science and Technology, Taiwan (MOST-104-2628-M-002-012) and the National Taiwan University (NTU-104R890913 and NTU-105R8956-2).

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Authors and Affiliations

  1. Department of Chemistry, National Taiwan University, Taipei, Taiwan

    Jia-Cheng Chang, Shin-Han Tseng, Yi-Hung Liu, Shie-Ming Peng & Sheng-Hsien Chiu

  2. Institute of Molecular Biology, National Chung Hsing University, Taichung, Taiwan

    Chien-Chen Lai

  3. Department of Medical Genetics, China Medical University Hospital, Taichung, Taiwan

    Chien-Chen Lai

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  1. Jia-Cheng Chang
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Contributions

J.-C.C. and S.-H.C. conceived and designed the experiments. J.-C.C. and S.-H.T. completed the synthesis. C.-C.L. performed the mass spectral analysis. Y.-H.L. solved the crystal structures under the supervision of S.-M.P. J.-C.C. and S.-H.C. co-wrote the manuscript and analysed the data. S.-H.C. directed the study.

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Correspondence to Sheng-Hsien Chiu.

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Supplementary information

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Supplementary information (PDF 15865 kb)

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Crystallographic data for compound 1. (CIF 1975 kb)

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Crystallographic data for compound 3. (CIF 2017 kb)

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Crystallographic data for compound 8. (CIF 4016 kb)

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Crystallographic data for compound 9. (CIF 2397 kb)

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Chang, JC., Tseng, SH., Lai, CC. et al. Mechanically interlocked daisy-chain-like structures as multidimensional molecular muscles. Nature Chem 9, 128–134 (2017). https://doi.org/10.1038/nchem.2608

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