TY - JOUR
T1 - 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
AU - Matsumoto, Takuya
AU - Kominami, Tsuyoshi
AU - Ueda, Kazumasa
AU - Sugimoto, Toyonari
AU - Tada, Toshiji
AU - Yoshino, Harukazu
AU - Murata, Keizo
AU - Shiro, Motoo
AU - Negishi, Ei Ichi
AU - Matsui, Hiroshi
AU - Toyota, Naoki
AU - Endo, Satoshi
AU - Takahashi, Kazuko
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Priority Areas (B) (No. 1224209) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
PY - 2002/11/1
Y1 - 2002/11/1
N2 - 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 me V). 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.
AB - 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 me V). 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.
KW - Charge-transfer salt
KW - High electrical conductivity
KW - Magnetic anion
KW - New donor molecule
KW - Semiconducting
KW - Very small π-d interaction
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U2 - 10.1006/jssc.2002.9688
DO - 10.1006/jssc.2002.9688
M3 - Article
AN - SCOPUS:0036870006
SN - 0022-4596
VL - 168
SP - 408
EP - 417
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
IS - 2
ER -