Phase transition of unsymmetric bis(quaternary alkyl bromide) salts of 1,4-diazabicyclo(2.2.2)octane, C10-DABCO-Cn-Br2 (11.LEQ.n.LEQ.22).

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概要

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• Phase transitions of unsymmetric bis(quaternary alkyl bromide) salts of 1,4-diazabicyclo[2.2.2]octane (DABCO)(C<SUB>10</SUB>–DABCO–C<I><SUB>n</SUB></I>–Br<SUB>2</SUB>, 11≤<I>n</I>≤22) were studied on the basis of measurements of differential scanning calorimetries, infrared absorption spectroscopy, and bromide-anion conductivities. The DSC measurements showed two transition temperatures (<I>T</I><SUB>c1</SUB> and <I>T</I><SUB>c2</SUB>, <I>T</I><SUB>c1</SUB>><I>T</I><SUB>c2</SUB>); this exhibits the existence of the metastable phase for the DABCO salts (C<SUB>10</SUB>–DABCO–C<I><SUB>n</SUB></I>-Br<SUB>2</SUB>, 12≤<I>n</I>≤22). The metastable phase was converted to the stable phase within several days except for C<SUB>10</SUB>–DABCO–C<I><SUB>n</SUB></I>–Br<SUB>2</SUB> (<I>n</I>=12, 22). The temperature dependence of the infrared absorption spectra revealed that the band progressions due to two different alkyl chains disappeared at <I>T</I><SUB>c1</SUB> and appeared again at <I>T</I><SUB>c2</SUB>. This shows that the <I>trans</I>-zigzag conformation of the alkyl chains in the low temperature phase is destroyed by the conformational change above <I>T</I><SUB>c1</SUB> and then recovered again below <I>T</I><SUB>c2</SUB>. Abrupt increases in the bromide-anion conductivities by 100–1380 times were observed at around <I>T</I><SUB>c2</SUB> for the samples annealed beforehand above <I>T</I><SUB>c1</SUB>. However, the virgin samples showed much broader increases in the conductivities below <I>T</I><SUB>c1</SUB>; no conductivity jump was observed. The conductivity increase was caused by the conformational change in the alkyl groups. The concomitant formations of the voids facilitate the bromide-anion transport.

• 公益社団法人 日本化学会の論文

著者

• Shimizu Jun

  Department Of Clinical Dietetics And Human Nutrition Faculty Of Pharmaceutical Sciences Josai Univer

• Mikawa Hiroshi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Nogami Takashi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Imamura Kengo

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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