Skip to main content
SpringerLink
Log in

New ferroelectric: Bis-thiourea pyridinium bromide inclusion compound

  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

Dielectric measurements (permittivity and hysteresis loop) of monocrystals of bis-thiourea pyridinium bromide inclusion compound have revealed for the first time ferroelectric properties of the studied samples. In the present article, a model of ferroelectric ordering on the basis of single-crystal x-ray diffraction data is described. In the low-temperature phase, the spontaneous polarization is directed along the a axis and ferroelectricity is of the mixed type (displacement and order-disorder component), whereas in the intermediate phase the spontaneous polarization is directed along the c axis and ferroelectricity is of the order-disorder type.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

TABLE I
FIG. 1
FIG. 2
FIG. 3
FIG. 4
FIG. 5
FIG. 6
TABLE II

Similar content being viewed by others

REFERENCES

  1. J.F. Scott: Applications of modern ferroelectrics. Science 315, 954 (2007).

    Article  CAS  Google Scholar 

  2. C.H. Ahn, K.M. Rabe, and J.M. Triscone: Ferroelectricity at the nanoscale: Local polarization in oxide thin films and heterostructures. Science 303, 488 (2004).

    Article  CAS  Google Scholar 

  3. S. Horiuchi, Y. Tokunaga, G. Giovannetti, S. Picozzi, H. Itoh, R. Shimano, R. Kumai, and Y. Tokura: Above-room-temperature ferroelectricity in a single-component molecular crystal. Nature 463, 789 (2010).

    Article  CAS  Google Scholar 

  4. S. Horiuchi, F. Ishii, R. Kumail, Y. Okimoto, H. Tachibana, N. Nagaosa, and T. Yoshinori: Ferroelectricity near room temperature in cocrystals of nonpolar organic molecules. Nat. Mater. 4, 163 (2005).

    Article  CAS  Google Scholar 

  5. B.B. Van Aken, T.T. Palstra, A. Filippetti, and N.A. Spaldi: The origin of ferroelectricity in magnetoelectric YMnO3. Nat. Mater. 3, 164 (2004).

    Article  CAS  Google Scholar 

  6. M. Szafrański: Simple guanidinium salts revisited: Room–temperature ferroelectricity in hydrogen-bonded supramolecular structures. J. Phys. Chem. B 115, 8755 (2011).

    Article  CAS  Google Scholar 

  7. A. Katrusiak and M. Szafrański: Ferroelectricity in NH...N hydrogen bonded crystals. Phys. Rev. Lett. 82, 576 (1999).

    Article  CAS  Google Scholar 

  8. M. Szafranski and M. Jarek: From nonpolar to ferroelectric crystal structure: The temperature-tuned growth of two guanidinium ethoxysulfonate polymorphs. J. Phys. Chem. B 112, 3101 (2008).

    Article  CAS  Google Scholar 

  9. P. Czarnecki, W. Nawrocik, Z. Pajak, and J. Wasicki: Ferroelectric properties of pyridinium tetrafluoroborate. Phys. Rev. B 49, 1511 (1994).

    Article  CAS  Google Scholar 

  10. P. Czarnecki, W. Nawrocik, Z. Pajak, and J. Wasicki: Ferroelectric properties of pyridinium perchlorate. J. Phys. Condens. Matter 6, 4955 (1994).

    Article  CAS  Google Scholar 

  11. J. Wasicki, P. Czarnecki, Z. Pajak, W. Nawrocik, and W. Szczepański: Ferroelectric properties of pyridinium perrhenate. J. Chem. Phys. 107, 576 (1997).

    Article  CAS  Google Scholar 

  12. Z. Pajak, P. Czarnecki, J. Wasicki, and W. Nawrocik: Ferroelectric properties of pyridinium periodate. J. Chem. Phys. 109, 6420 (1998).

    Article  CAS  Google Scholar 

  13. H. Maluszynska, P. Czarnecki, S. Lewicki, J. Wasicki, and M. Daniec: Structure and dynamics of ferroelectric pyridinium periodate. J. Phys. Condens. Matter 13, 11053 (2001).

    Article  CAS  Google Scholar 

  14. L. Bobrowicz-Sarga, P. Czarnecki, S. Lewicki, I. Natkaniec, W. Nawrocik, and J. Wasicki: Phase transitions in ferroelectric pyridinium periodide under high pressure. Phase Transitions 80, 725 (2007).

    Article  CAS  Google Scholar 

  15. Z. Pajak, P. Czarnecki, H. Maluszynska, B. Szafranska, and M. Szafran: Ferroelectric properties of pyridinium fluorosulfonate. J. Chem. Phys. 113, 848 (2000).

    Article  CAS  Google Scholar 

  16. Z. Pajak, H. Maluszynska, and P. Czarnecki: Crystal structure, molecular dynamics, and polar properties of pyridinium fluorochromate. J. Chem. Phys. 117, 5303 (2002).

    Article  CAS  Google Scholar 

  17. J. Przesławski, J. Jamiński, and Z. Czapla. Specific heat anomalies in ferroelectric PyBF4. Ferroelectrics 363, 64 (2008).

    Article  CAS  Google Scholar 

  18. J. Hatori, M. Komukae, Z. Czapla, and T. Osaka: Dielectric dispersion studies in pyridinium periodate single crystal. J. Phys. Soc. Jpn. 71, 1431 (2002).

    Article  CAS  Google Scholar 

  19. M. Hanaya, H. Shibazaki, M. Oguni, T. Nemoto, and Y. Ohashi: Orientational ordering/disordering of ions accompanied by phase transitions in pyridinium tetrafluoroborate crystal. J. Phys. Chem. Solids 61, 651 (2000).

    Article  CAS  Google Scholar 

  20. B. Beck, K. Muller, and E. Roduner: 2H NMR study of dynamics, ordering, and phase transitions in ferroelectric pyridinium tetrafluoroborate. Chem. Mater. 15, 1739 (2003).

    Article  CAS  Google Scholar 

  21. J. Józków, R. Jakubas, and J. Baran: Infrared investigation of the order–disorder phase transitions in (C5H5NH)6Bi4Cl18. J. Mol. Struct. 555, 273 (2000).

    Article  Google Scholar 

  22. J. Wasicki, A. Pajzderska, and Z. Fojud: Temperature dependence of spontaneous polarization in order−disorder pyridinium periodate extracted from 2H NMR data. J. Phys. Chem. C 112, 7503 (2008).

    Article  CAS  Google Scholar 

  23. J. Jozkow, W. Medycki, J. Zaleski, R. Jakubas, G. Bator, and Z. Ciunik: Structure, phase transition and molecular motions in (C5H5NH)BiCl4. Phys. Chem. Chem. Phys. 3, 3222 (2001).

    Article  CAS  Google Scholar 

  24. M. Maeda, K. Okada, K. Deguchi, M. Iwata, and I. Suzuki: Dielectric dispersion of pyridinium tetrafluoroborate single crystals. J. Phys. Soc. Jpn. 74, 1416 (2005).

    Article  CAS  Google Scholar 

  25. M. Hanaya, M. Nomoto, T. Miura, and M. Oguni: Discovery of dipolar-glassy state in a newly found solid–solution system of C5NH6(BF4)1−x(PF6)x. Solid State Commun. 115, 57 (2000).

    Article  CAS  Google Scholar 

  26. K. Prout, S.J. Heyes, C.M. Dobson, A. McDaid, T. Maris, M. Muller, and M.J. Seaman: Variable-temperature studies of order/disorder transitions in the thiourea pyridinium halide crystals by XRD and solid-state 2H NMR. Chem. Mater. 12, 3561 (2000).

    Article  CAS  Google Scholar 

  27. H. Maluszynska and P. Czarnecki: Structure, phase transitions and dielectric properties of a new inclusion compound of bis-thiourea pyridinium nitrate salt. Z. Kristallogr. 221, 218 (2006).

    CAS  Google Scholar 

  28. A. Pajzderska, J. Wasicki, P. Czarnecki, L. Toupet, and E. Collet: Discovery of an intermediate phase in bis-thiourea pyridinium chloride inclusion compound. J. Chem. Phys. 130, 044503 (2009).

    Article  CAS  Google Scholar 

  29. H. Maluszynska, P. Czarnecki, Z. Fojud, and J. Wasicki: Redetermination of the structure and dielectric properties of bis(thiourea) pyridinium iodide–a new ferroelectric inclusion compound. Acta Crystallogr., Sect. B: Struct. Sci. 64(5), 572 (2008).

    Article  CAS  Google Scholar 

  30. A. Pajzderska, M.A. Gonzalez, J.P. Embs, and J. Wasicki: Complex dynamics of pyridinium cation in ferroelectric bis(thiourea)pyridinium iodide studied by quasielastic neutron scattering. J. Phys. Chem. C 115, 15164 (2011).

    Article  CAS  Google Scholar 

  31. A. Pajzderska, M.A. Gonzalez, and J. Wasicki: Molecular dynamics simulation of cation dynamics in bis-thiourea pyridinium nitrate inclusion compound. J. Chem. Phys. 135, 074508 (2011).

    Article  CAS  Google Scholar 

  32. A. Pajzderska, M.A. Gonzalez, and J. Wasicki: In-plane pyridinium cation reorientation in bis-thiourea chloride, bromide and iodide: Quasielastic neutron scattering combined with molecular dynamics simulations. Phys. Chem. Chem. Phys. 14, 3949 (2012).

    Article  CAS  Google Scholar 

  33. M. Grottel, A. Kozak, A. Pajzderska, W. Szczepanski, and J. Wasicki: 1H NMR study of molecular motions in thiourea pyridinium nitrate inclusion compound. Z. Naturforsch., A 59, 505 (2004).

    Article  CAS  Google Scholar 

  34. M. Grottel, A. Pajzderska, and J. Wasicki: 1H NMR study of molecular motions in thiourea pyridinium halide inclusion compounds. Z. Naturforsch., A 58, 638 (2003).

    Article  CAS  Google Scholar 

  35. A. Pajzderska, Z. Fojud, R. Goc, and J. Wasicki: Cation dynamics in pyridinium nitrate and bis-thiourea pyridinium nitrate inclusion compound studied by 2H NMR spectroscopy. J. Phys. Condens. Matter 19, 156220 (2007).

    Article  CAS  Google Scholar 

  36. A. Marczak, P. Czarnecki, and S. Mielcarek: Dielectric spectroscopy of (bis)thiourea pyridinium bromide. Z. Naturforsch., A 59, 857 (2004).

    Article  CAS  Google Scholar 

  37. A. Pajzderska, M.A. Gonzalez, and J. Wasicki: Quasielastic neutron scattering study of pyridinium cation reorientation in thiourea pyridinium nitrate inclusion compound. J. Chem. Phys. 128, 084507 (2008).

    Article  CAS  Google Scholar 

  38. A. Pajzderska, P. Czarnecki, J.P. Embs, M.A. Gonzalez, F. Juranyi, J. Krawczyk, B. Peplinska, and J. Wasicki: A study of out-of-plane cation dynamics in a bis-thiourea pyridinium chloride inclusion compound. Phys. Chem. Chem. Phys. 13, 8908 (2011).

    Article  CAS  Google Scholar 

  39. A. Pajzderska, E. Collet, P. Czarnecki, and J. Wasicki: Ferroelectricity of inclusion compounds of thiourea with pyridinium iodide and nitrate. J. Phys. Chem. C 113, 6282 (2009).

    Article  CAS  Google Scholar 

  40. M.R. Truter and B.L. Vickery: The crystal structure of bisthiourea pyridinium bromide. Acta Crystallogr., Sect. B 28, 387 (1972).

    Article  CAS  Google Scholar 

  41. W.K. Lee and H.Z. Cummins: Raman activation of acoustic modes in commensurate A2BX4 crystals by zone folding. Phys. Rev. B 39, 4457 (1989).

    Article  CAS  Google Scholar 

  42. A.S. Gibbs, K.S. Knight, and P. Lightfoot: High-temperature phase transitions of hexagonal YMnO3. Phys. Rev. B 83, 094111 (2011).

    Article  CAS  Google Scholar 

Download references

ACKNOWLEDGMENTS

This work has been partially financed by the Ministry of Science and Higher Education of Poland, Grant No. 202 032937, and supported by Rennes Region Bretagne (CREATE Ultimate 4146).

Author information

Authors and Affiliations

  1. Faculty of Physics, Adam Mickiewicz University, 61-614, Poznan, Poland

    Piotr Czarnecki & Aleksandra Pajzderska

  2. Institut de Physique de Rennes, Université de Rennes 1, UMR UR1-CNRS 6251, F-35000, Rennes, France

    Eric Collet & Loic Toupet

  3. Faculty of Physics, Adam Mickiewicz University, 61-614, Poznan, Poland

    Jan Wąsicki

Authors
  1. Piotr Czarnecki
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Aleksandra Pajzderska
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Eric Collet
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Loic Toupet
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jan Wąsicki
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jan Wąsicki.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Czarnecki, P., Pajzderska, A., Collet, E. et al. New ferroelectric: Bis-thiourea pyridinium bromide inclusion compound. Journal of Materials Research 27, 2844–2850 (2012). https://doi.org/10.1557/jmr.2012.301

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2012.301

Search

Navigation