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Molecular motor-driven abrupt anisotropic shape change in a single crystal of a Ni complex

Abstract

Many molecular machines with controllable molecular-scale motors have been developed. However, transmitting molecular movement to the macroscopic scale remains a formidable challenge. Here we report a single crystal of a Ni complex whose shape changes abruptly and reversibly in response to thermal changes at around room temperature. Variable-temperature single-crystal X-ray diffraction studies show that the crystalline shape change is induced by an unusual 90° rotation of uniaxially aligned oxalate molecules. The oxalate dianions behave as molecular-scale rotors, with their movement propagated through the entire crystalline material via intermolecular hydrogen bonding. Consequently, the subnanometre-scale changes in the oxalate molecules are instantly amplified to a micrometre-scale contraction or expansion of the crystal, accompanied by a thermal hysteresis loop. The shape change in the crystal was clearly detected under an optical microscope. The large directional deformation and prompt response suggest a role for this material in microscale or nanoscale thermal actuators.

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Figure 1: Crystal structures of 1 at different temperatures.
Figure 2: Temperature dependence of differential scanning calorimetry and heat capacity for 1.
Figure 3: Crystal deformation induced by ox2− reorientation.

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Acknowledgements

This work was supported by a KAKEN on Innovative Areas (‘Soft Molecular Systems’ Area 2503, No. 26104528) from MEXT (Japan). Z-S.Y. thanks the China Scholarship Council for support.

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Authors and Affiliations

Authors

Contributions

Z-S.Y. and O.S. designed the study, conducted experiments and wrote most of the paper. M.M. and S. Kang assisted in measuring the change in crystal shape. K.T., K.Z. and S. Kanegawa contributed to the diffraction studies. T.K., Y.S. and K.Y. performed the calculations and wrote the related discussion. N.A. and Y.M. performed the heat-capacity measurements. T.N. contributed to analyses of the molecular motion. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Osamu Sato.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 5509 kb)

Supplementary video

Supplementary video 1 (MOV 575 kb)

Supplementary video

Supplementary video 2 (MOV 445 kb)

Supplementary information

Crystallographic data for compound 1 at 243 K, LT phase. (CIF 283 kb)

Supplementary information

Crystallographic data for compound 1 at 263 K, HT phase. (CIF 77 kb)

Supplementary information

Crystallographic data for compound 1 at 263 K, LT phase. (CIF 281 kb)

Supplementary information

Crystallographic data for compound 1 at 283 K, HT phase. (CIF 137 kb)

Supplementary information

Crystallographic data for compound 2 at 223 K, LT phase. (CIF 322 kb)

Supplementary information

Crystallographic data for compound 2 at 293 K, HT phase. (CIF 103 kb)

Supplementary information

Crystallographic data for compound 3 at 200 K, LT phase. (CIF 634 kb)

Supplementary information

Crystallographic data for compound 3 at 288 K, HT phase. (CIF 130 kb)

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Yao, ZS., Mito, M., Kamachi, T. et al. Molecular motor-driven abrupt anisotropic shape change in a single crystal of a Ni complex. Nature Chem 6, 1079–1083 (2014). https://doi.org/10.1038/nchem.2092

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