The phase transition of 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides, Cn-DABCO-Br(11.LEQ.n.LEQ.22).

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概要

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• The phase transitions of a series of 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides were studied on the basis of DSC, measurements of the ionic conductivities of the bromide anion, and Raman spectroscopy. Two endothermic signals were observed at the temperatures of <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>) for most of the materials. The transition enthalpies and transition entropies were not very different for the transitions at <I>T</I><SUB>c1</SUB>, irrespective of the alkyl-chain lengths attached to DABCO nitrogens. On the other hand, these values tended to increase with an increase in the alkyl-chain lengths for the transitions at <I>T</I><SUB>c2</SUB>. The temperature dependences of the ionic conductivities of the bromide anion showed abrupt increases in the conductivities by a factor of 2–10. The conductivity jumps were observed around <I>T</I><SUB>c2</SUB>. The temperature dependences of the Raman spectra gave detailed information on the phase transition; (1) the change in the subcell structure took place at <I>T</I><SUB>c1</SUB>, with the concomitant occurrence of a conformational change in the alkyl group; (2) above <I>T</I><SUB>c2</SUB>, the alkyl chain takes a liquid-like disordered form, and a rotational motion of the DABCO portion sets in.

著者

• Kobayashi Masamichi

  Department Of Macromolecular Science Faculty Of Science Osaka University

• Shirota Yasuhiko

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Ishioka Tsutomu

  Department Of Chemistry Faculty Of Science Toyama University

• Nogami Takashi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Imamura Kengo

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Kobayashi Masamichi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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