Tetrachloroferrate (III) Salts of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] and BDA-TTP [2,5-Bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene]: Crystal Structures and Physical Properties |
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Authors: | Koichi KikuchiHiroyuki Nishikawa Isao IkemotoTakashi Toita Hiroki AkutsuShin'ichi Nakatsuji Jun-ichi Yamada |
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Institution: | a Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo, 192-0397, Japanb Department of Material Science, Graduate School of Science, Himeji Institute of Technology, 3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo, 678-1297, Japan |
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Abstract: | Three FeCl4 salts based on non-tetrathiafulvalene (TTF) donors, 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) and 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), have been prepared and characterized as κ-(BDH-TTP)2FeCl4, β-(BDA-TTP)2FeCl4, and (BDA-TTP)3FeCl4 · PhCl. The κ-(BDH-TTP)2FeCl4 salt, with a room-temperature conductivity (σrt) of 39 S cm−1, is metallic down to 1.5 K, and its magnetic susceptibility obeys the Curie-Weiss law with a Curie constant (C) of 4.25 emu K mol−1 and a Weiss constant (θ) of 0.041 K. β-(BDA-TTP)2FeCl4 exhibits metallic behavior (σrt=9.4 S cm−1) with a sharp metal-to-insulator (MI) transition (TMI=113 K) and antiferromagnetic ordering with the Néel temperature of near 8.5 K, whereas the solvated (BDA-TTP)3FeCl4 · PhCl salt is a semiconductor with a thermal activation energy of 0.11 eV (σrt=2.0× 10−2 S cm−1) and exhibits Curie-Weiss behavior (C=4.42 emu K mol−1, θ=−0.35 K). |
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Keywords: | non-TTF donor crystal structure conductivity magnetic susceptibility metallic behavior antiferromagnetic ordering |
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