The phase transitions of 1,4-dialkyl-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), Cn-DABCO-Cn-(BF4)2 (10.LEQ.n.LEQ.22).

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概要

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• The phase transitions of a series of title compounds were investigated by means of DSC, IR absorption spectra, and measurements of ionic conductivities. All of the compounds exhibited phase transitions in the range of 77–110 °C. The IR absorption spectra clarified that conformational change in the alkyl chain occurred above the transition temperature. The temperature dependences of the ionic conductivities of BF<SUB>4</SUB><SUP>−</SUP> showed conductivity jumps by a factor of 9–120 around the transition temperatures. A comparison of the DSC results and the ionic conductivities of BF<SUB>4</SUB>-salts with those of the corresponding Br-salts showed that the former compounds have higher transition temperatures, smaller transition enthalpies (and, accordingly, smaller transition entropies), and smaller values of the conductivity jumps than the latter. These results show that BF<SUB>4</SUB>-salts are more rigid than Br-salts in the low temperature phase and that the motion of the alkyl group of the former salts is less vigorous than the latter in the high-temperature phase. By observing the crystal with a polarization microscope under crossed Nicols condition, it was found that optical anisotropy was diminished gradually with the elevation of the temperature and disappeared completely above <I>T</I><SUB>c</SUB> without changing the crystal shape.

• 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

• Shirota Yasuhiko

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Nogami Takashi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Terada Tohru

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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