Crystal Structures, and Electrical Conducting and Magnetic Properties in the Plate Crystals of (Ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)2·MX4 (M=Fe, Ga, X=Br; M=Fe, X=C1) Salts |
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Authors: | Takuya MatsumotoTsuyoshi Kominami Kazumasa UedaToyonari Sugimoto Toshiji TadaHarukazu Yoshino Keizo MurataMotoo Shiro Ei-ichi NegishiHiroshi Matsui Naoki Toyota Satoshi EndoKazuko Takahashi |
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Institution: | a Research Institute for Advanced Science and Technology, Osaka, Prefecture University, Osaka, 599-8570, Japanb Center for Interdisciplinary Research, Tohoku University, Sendai, 980-8577, Japanc Graduate School of Science, Osaka City University, Osaka, 558-8585, Japand Rigaku Corporation, Tokyo, 196-8666, Japane Graduate School of Science, Tohoku University, Sendai, 980-8578, Japanf Center for Low-Temperature Science, Tohoku University, Sendai, 980-8577, Japan |
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Abstract: | By the reaction of a new donor molecule, ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr3, GaBr3 or FeCl3 in CH3CN/CS2 charge transfer (CT) salts of 1 with counteranions of FeBr4−, GaBr4− or FeCl4− (12·FeBr4, 12·GaBr4 and 12·FeCl4) as plate crystals were obtained. Their crystal structures are apparently similar to each other, in which 1 molecules are dimerized in the parallel direction of their molecular long axes, and the dimers are stacked with changing the direction of the molecular long axes alternately to form a one- dimensional column. The counteranions intervene between the 1-stacked columns and are aligned in a zigzag manner. The room-temperature electrical conductivities of 12·FeBr4 and 12·GaBr4 are fairly high (10-15 S cm−1), but a small value (0.8 S cm−1) is obtained for 12·FeCl4. For all CT salts, temperature dependences of electrical conductivity are semiconducting in spite of very small activation energies (30-90 meV). Based on the comparison between their electrical conducting and magnetic properties, it is suggested that the d spins of FeBr4− or FeCl4− ions exert almost no influence on the π conducting electrons in the 1-stacked column. |
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Keywords: | new donor molecule charge-transfer salt magnetic anion high electrical conductivity semiconducting very small π-d interaction |
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