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

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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
Issue number37
Publication statusPublished - Sep 21 2016


All Science Journal Classification (ASJC) codes

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

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