The phase transition of 1,4-dialkyl-1,4-diazoniabicyclo[2.2.2]octane dibromides, Cn-DABCO-Cn+1-Br2 (10.LEQ.n.LEQ.17)

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概要

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• The phase transitions of 1,4-dialkyl-1,4-diazoniabicyclo[2.2.2]octane dibromide (bis(quaternary alkyl bromide salts) of DABCO) in which the difference in the carbon numbers of the two alkyl groups is one, were studied on the basis of measurements of differential scanning calorimetry, infrared absorption spectroscopy, and bromide-anion conductivities. The DSC measurements showed that an endothermic transition occurred at <I>T</I><SUB>c1</SUB> when the sample was heated from room temperature. An exothermic transition occurred at <I>T</I><SUB>c2</SUB>(<I>T</I><SUB>c2</SUB><T<SUB>c1</SUB>) when the sample was cooled after it had been heated above <I>T</I><SUB>c1</SUB>. The transition temperatures (<I>T</I><SUB>c1</SUB> and <I>T</I><SUB>c2</SUB>), the transition enthalpies, and the transition entropies increased as the increase in the alkyl-chain lengths. <I>T</I><SUB>c1</SUB> was found to be governed by the even numbers of the alkyl group. The temperature dependence of the IR absorption spectra showed that the <I>trans</I>-zigzag conformation of the alkyl chain was destroyed by a conformational change above <I>T</I><SUB>c1</SUB>, and that the annealed sample existed as a metastable phase. The temperature dependence of the bromide-anion conductivities showed abrupt increases in the conductivities by three orders of magnitude at around the transition temperatures. The temperatures of the conductivity jump of the virgin samples were usually higher than those of the annealed samples. The differences in these two temperatures tended to become smaller as the increase in the alkyl-chain lengths. This fact can be explained as that the solid-state properties of the unsymmetric bis(quaternary salts) of DABCO tend to resemble those of the symmetric bis(quaternary salts) of DABCO as the increase in the alkyl-chain lengths.

• 公益社団法人 日本化学会の論文

著者

• Shirota Yasuhiko

  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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