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Ferroelectricity and polarity control in solid-state flip-flop supramolecular rotators

Nature Materials volume 8, pages 342–347 (2009)Cite this article

Abstract

Molecular rotation has attracted much attention with respect to the development of artificial molecular motors, in an attempt to mimic the intelligent and useful functions of biological molecular motors. Random motion of molecular rotators—for example the 180∘ flip-flop motion of a rotatory unit—causes a rotation of the local structure. Here, we show that such motion is controllable using an external electric field and demonstrate how such molecular rotators can be used as polarization rotation units in ferroelectric molecules. In particular, m-fluoroanilinium forms a hydrogen-bonding assembly with dibenzo[18]crown-6, which was introduced as the counter cation of [Ni(dmit)2]− anions (dmit2−=2-thioxo-1,3-dithiole-4,5-dithiolate). The supramolecular rotator of m-fluoroanilinium exhibited dipole rotation by the application of an electric field, and the crystal showed a ferroelectric transition at 348 K. These findings will open up new strategies for ferroelectric molecules where a chemically designed dipole unit enables control of the nature of the ferroelectric transition temperature.

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Figure 1: Crystal structure and molar magnetic susceptibility (χmol) of (m-FAni+)(DB[18]crown-6) [Ni(dmit)2]− (salt 1).
Figure 2: Dielectric properties of salts 1 and 2.
Figure 3: Molecular rotation of the m-FAni+ cation in salt 1.
Figure 4: Average structure of (m-FAni+)(DB[18]crown-6) in salt 1.

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References

  1. Thomas, H. & Mueller, K. A. Structural Phase Transition I (Springer, 1981).

    Google Scholar 

  2. Lines, M. E. & Glass, A. M. Principles and Applications of Ferroelectrics and Related Materials 293–327 (Clarendon, 1977).

    Google Scholar 

  3. Johnson, R. D. et al. C60 rotation in the solid state: Dynamics of a faceted spherical top. Science 255, 1235–1238 (1992).

    Article  CAS  Google Scholar 

  4. Stryer, L. Biochemistry 4th edn391–411 (Freeman, 1995).

    Google Scholar 

  5. Kelly, T. R., De Silva, H. & Silva, R. A. Unidirectional rotary motion in a molecular system. Nature 401, 150–152 (1999).

    Article  CAS  Google Scholar 

  6. Koumura, N. et al. Light-driven monodirectional molecular rotor. Nature 401, 152–155 (1999).

    Article  CAS  Google Scholar 

  7. Leigh, D. A., Wong, J. K. Y., Dehez, F. & Zerbetto, F. Unidirectional rotation in a mechanically interlocked molecular rotor. Nature 424, 174–179 (2003).

    Article  CAS  Google Scholar 

  8. Kottas, G. S. et al. Artificial molecular rotors. Chem. Rev. 105, 1281–1376 (2005).

    Article  CAS  Google Scholar 

  9. Kay, E. R., Leigh, D. A. & Zerbetto, F. Synthetic molecular motors and mechanical machines. Angew. Chem. Int. Ed. 46, 72–191 (2007).

    Article  CAS  Google Scholar 

  10. Nakamura, T. et al. A molecular metal with ion-conducting channels. Nature 394, 159–160 (1998).

    Article  CAS  Google Scholar 

  11. Akutagawa, T., Takeda, S., Hasegawa, T. & Nakamura, T. Proton-transfer and dielectric phase transition in molecular conductor (HDABCO+)2(TCNQ)3 . J. Am. Chem. Soc. 126, 291–294 (2004).

    Article  CAS  Google Scholar 

  12. Sherwood, J. N. (ed.) The Plastically Crystalline State (Wiley, 1979).

  13. Garcia-Garibay, M. A. Crystalline molecular machines: Encoding supramolecular dynamics into molecular structure. Proc. Natl Acad. Sci. 102, 10771–10776 (2005).

    Article  CAS  Google Scholar 

  14. Horansky, R. D. et al. Dielectric response of a dipolar molecular rotor crystal. Phys. Rev. B 72, 014302 (2005).

    Article  Google Scholar 

  15. Nishihara, S. et al. Multirotations of (anilinium+)([18]crown-6) supramolecular cation structure in magnetic [Ni(dmit)2]− salt. Chem. Asian J. 2, 1083–1090 (2007).

    CAS  Google Scholar 

  16. Sato, D. et al. Supramolecular rotor of adamantylammonium([18]crown-6) in [Ni(dmit)2]− salt. Inorg. Chem. 46, 363–365 (2007).

    Article  CAS  Google Scholar 

  17. Akutagawa, T. et al. Solid state molecular rotators of anilinium and adamantylammonium in [Ni(dmit)2]− salts with diverse magnetic properties. Inorg. Chem. 47, 5951–5962 (2008).

    Article  CAS  Google Scholar 

  18. Horiuchi, S. et al. Ferroelectricity near room temperature in co-crystals of nonpolar organic molecules. Nature Mater. 4, 163–166 (2005).

    Article  CAS  Google Scholar 

  19. Katrusiak, A. & Szafrański, M. Ferroelectricity in NH–N hydrogen bonded crystals. Phys. Rev. Lett. 82, 576–579 (1999).

    Article  CAS  Google Scholar 

  20. Horiuchi, S. & Tokura, Y. Organic ferroelectrics. Nature Mater. 7, 357–366 (2008).

    Article  CAS  Google Scholar 

  21. Desiraju, G. R. & Steiner, T. The Weak Hydrogen Bond 122–292 (Oxford Univ. Press, 1999).

    Google Scholar 

  22. Kao, K. C. Dielectric Phenomena in Solids (Elsevier, 2004).

    Google Scholar 

Download references

Acknowledgements

This work was supported in part by a Grant-in-Aid for Science Research from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. We would like to thank J. Kawamata and H. Yamaki (Yamaguchi Univ.) for conducting the second harmonic generation measurements.

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Authors and Affiliations

  1. Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan

    Tomoyuki Akutagawa, Shin-Ichiro Noro & Takayoshi Nakamura

  2. Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0810, Japan

    Tomoyuki Akutagawa, Hiroyuki Koshinaka, Daisuke Sato, Shin-Ichiro Noro & Takayoshi Nakamura

  3. CREST, Japan Science and Technology Agency (JST), Kawaguchi 332-0012, Japan

    Tomoyuki Akutagawa & Takayoshi Nakamura

  4. Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan

    Sadamu Takeda

  5. Correlated Electron Research Center, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8562, Japan

    Hiroyuki Takahashi, Reiji Kumai & Yoshinori Tokura

Authors
  1. Tomoyuki Akutagawa
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  2. Hiroyuki Koshinaka
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  3. Daisuke Sato
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  4. Sadamu Takeda
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  6. Hiroyuki Takahashi
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  7. Reiji Kumai
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  8. Yoshinori Tokura
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  9. Takayoshi Nakamura
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Contributions

T.A. and T.N. planned the project and carried out experimental work with the other authors. H.K., D.S. and S.-I.N. carried out sample preparation, structural analysis and electrical measurements. S.T. conducted measurements of temperature-dependent NMR spectra. R.K., H.T. and Y.T. carried out the synchrotron radiation X-ray crystal structural analysis at the High Energy Accelerator Research Organization.

Corresponding authors

Correspondence to Tomoyuki Akutagawa or Takayoshi Nakamura.

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Akutagawa, T., Koshinaka, H., Sato, D. et al. Ferroelectricity and polarity control in solid-state flip-flop supramolecular rotators. Nature Mater 8, 342–347 (2009). https://doi.org/10.1038/nmat2377

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