Above Room Temperature Organic Ferroelectrics

Diprotonated 1,4-Diazabicyclo[2.2.2]octane Shifts between Two 2-Chlorobenzoates

Zi Shuo Yao, Kaoru Yamamoto, Hong Ling Cai, Kazuyuki Takahashi, Osamu Sato

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

A pure organic single crystal, [H2dabco]·[2CB]2 ([H2dabco]2+ = diprotonated 1,4-diazabicyclo[2.2.2]octane, 2CB- = 2-chlorobenzoate), which undergoes a ferroelectric-to-paraelectric phase transition above room temperature (∼323 K upon heating), was prepared and characterized. This ferroelectric crystal possesses a distinctive supramolecular architecture composed of discrete H-bonded trimeric units (two 2CB- anions bridged by one [H2dabco]2+ cation through N-H···O hydrogen bond interactions). In the paraelectric phase, the [H2dabco]2+ cation is rotationally disordered and lies at the symmetric center of the trimer. Upon cooling, it is frozen in an ordered state and deviates toward a 2CB- anion at one end along the H-bond. The collective displacement of the cations leads to a polarization of the single crystal along the crystallographic c axis, which is confirmed by the temperature dependence of the second harmonic generation and spontaneous polarization. A significant increase in the phase transition temperature of the deuterated analogue suggests that the proton plays an important role in the ferroelectric phase transition.

Original languageEnglish
Pages (from-to)12005-12008
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number37
DOIs
Publication statusPublished - Sep 21 2016

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Phase Transition
Ferroelectric materials
Cations
Phase transitions
Positive ions
Temperature
Anions
Negative ions
Single crystals
Polarization
Transition Temperature
Harmonic generation
Heating
Superconducting transition temperature
Protons
Hydrogen
Hydrogen bonds
Cooling
Crystals
2-chlorobenzoic acid

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Above Room Temperature Organic Ferroelectrics : Diprotonated 1,4-Diazabicyclo[2.2.2]octane Shifts between Two 2-Chlorobenzoates. / Yao, Zi Shuo; Yamamoto, Kaoru; Cai, Hong Ling; Takahashi, Kazuyuki; Sato, Osamu.

In: Journal of the American Chemical Society, Vol. 138, No. 37, 21.09.2016, p. 12005-12008.

Research output: Contribution to journalArticle

Yao, Zi Shuo ; Yamamoto, Kaoru ; Cai, Hong Ling ; Takahashi, Kazuyuki ; Sato, Osamu. / Above Room Temperature Organic Ferroelectrics : Diprotonated 1,4-Diazabicyclo[2.2.2]octane Shifts between Two 2-Chlorobenzoates. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 37. pp. 12005-12008.
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