1:1 complexes of dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-dithiolemethides with CuBr2 as a new type of pi/d molecular system |
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Authors: | Iwamatsu M Kominami T Ueda K Sugimoto T Adachi T Fujita H Yoshino H Mizuno Y Murata K Shiro M |
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Institution: | Research Institute for Advanced Science and Technology, Osaka Prefecture University, Sakai, Osaka 599-8570, Japan. |
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Abstract: | The reaction of dimethylthio- (1) and ethylenedithio-tetrathiafulvalenothioquinone-1,3-dithiolemethides (2) with CuBr2 gave 1:1 complexes between the donors and CuBr2, 1.CuBr2 and 2.CuBr2, in which the Cu atom of CuBr2 binds to the thiocarbonyl S atom in 1 and 2. The electrical conductivity (sigma) of 1.CuBr2 at room temperature was ca. 10(-5) S cm-1, while a comparatively high value of 4.0 S cm-1 was obtained for 2.CuBr2, whose temperature dependence of sigma exhibited, however, semiconducting behavior with a very small activation energy of 0.18 eV. The observed paramagnetic susceptibilities (chi p's) of the Cu complexes were composed of both a component due to the localized Cu spins obeying the Curie-Weiss law and a temperature-independent chi p due to the conducting pi electrons on the 1- or 2-stacked columns. From the Curie constants obtained, the degrees of intramolecular electron transfer from 1 and 2 to CuBr2 moieties were estimated at ca. 90% and 60%, respectively. The small, negative Weiss temperature suggest very weak antiferromagnetic interactions among the Cu spins on the CuBr2 moieties. |
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