1:1 complexes of dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-dithiolemethides with CuBr2 as a new type of pi/d molecular system.
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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二甲硫基和亚乙基二硫基四硫富瓦烯硫醌-1,3-二硫代甲基化物与CuBr2的1:1配合物作为新型pi/d分子系统。
DOI：
10.1021/ic0001098
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发表时间：
2000
影响因子：
4.6
通讯作者：
M. Shiro
中科院分区：
文献类型：
--
作者：
M. Iwamatsu;T. Kominami;K. Ueda;T. Sugimoto;T. Adachi;H. Fujita;H. Yoshino;Y. Mizuno;K. Murata;M. Shiro
二甲硫基-（1）和乙撑二硫代四硫富瓦烯硫醌-1，3-二硫代甲基化物（2）与CuBr_2反应，生成了1：1的CuBr_2和2：1的CuBr_2配合物，其中CuBr_2的Cu原子与1和2中的硫代羰基S原子结合。在室温下，1.CuBr 2的电导率（σ）约为1.5%。10（-5）S cm-1，而2.CuBr_2的σ的温度依赖性表现出相对较高的值4.0 S cm-1，然而，半导体行为具有非常小的激活能0.18 eV。所观察到的顺磁磁化率（chi p的）的Cu配合物的组成部分，由于本地化的Cu自旋服从居里-外斯定律和温度无关的chi p由于1或2堆叠列上的导电π电子。从获得的居里常数，从1和2到CuBr 2部分的分子内电子转移的程度估计在约。90%和60%。小，负的韦斯温度表明非常弱的反铁磁相互作用之间的Cu自旋的CuBr 2部分。
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.