Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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

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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

References

  1. 1

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

    Google Scholar 

  2. 2

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

    Google Scholar 

  3. 3

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

    CAS  Article  Google Scholar 

  4. 4

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

    Google Scholar 

  5. 5

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

    CAS  Article  Google Scholar 

  6. 6

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

    CAS  Article  Google Scholar 

  7. 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).

    CAS  Article  Google Scholar 

  8. 8

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

    CAS  Article  Google Scholar 

  9. 9

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

    CAS  Article  Google Scholar 

  10. 10

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

    CAS  Article  Google Scholar 

  11. 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).

    CAS  Article  Google Scholar 

  12. 12

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

  13. 13

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

    CAS  Article  Google Scholar 

  14. 14

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

    Article  Google Scholar 

  15. 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. 16

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

    CAS  Article  Google Scholar 

  17. 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).

    CAS  Article  Google Scholar 

  18. 18

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

    CAS  Article  Google Scholar 

  19. 19

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

    CAS  Article  Google Scholar 

  20. 20

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

    CAS  Article  Google Scholar 

  21. 21

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

    Google Scholar 

  22. 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.

Author information

Affiliations

Authors

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.

Supplementary information

Supplementary Information

Supplementary Information (PDF 831 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing