Thermodynamic properties and phase transitions of methyltriphenylphosphonium and methyltriphenylarsonium bis(7,7,8,8-tetracyanoquinodimethanide)s and their solid solutions.

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概要

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• The heat capacities of stable organic free-radical salts [(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>PCH<SUB>3</SUB>]<SUB>1−<I>x</I></SUB><SUP>+</SUP>[(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>AsCH<SUB>3</SUB>]<I><SUB>x</SUB></I><SUP>+</SUP>(TCNQ)<SUB>2</SUB><SUP>\newdot</SUP> (<I>x</I>=0,0.159, 0.250, 0.449, and 1, and TCNQ=7,7,8,8-tetracyanoquinodimethane) have been measured with an adiabatic calorimeter in the temperature range between 12 and 370 K. The phase transitions are found for the former four cases at 315.65, 325.80, 333.05, and 357.92 K, respectively. The enthalpy and the entropy due to the phase transitions are determined. The transition temperature is raised by diluting the phosphonium salt with the arsonium one. This tendency is quite contrary to that found for usual solid solutions. The magnitude and the composition dependence of the transition entropy indicate that the phase transition of the solid solutions may be attributable to the changes in both the crystal structure and the magnetic spin state at the transition point. A plausible explanation for the present unusual tendency for the composition dependence is presented.

• 公益社団法人 日本化学会の論文

著者

• Seki Syuzo

  Department Of Chemistry Faculity Of Science Osaka University

• Sorai Michio

  Department Of Chemistry Faculty Of Science Osaka University

• Suga Hiroshi

  Department Of Chemistry Faculty Of Science Osaka University

• Kosaki Akio

  Department of Chemistry, Faculty of Science, Osaka University

• Suga Hiroshi

  Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University

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