Antiferromagnetic or Canted Antiferromagnetic Orderings of Fe(III) d Spins of FeX4- Ions in BEDT-TTFVO(S)·FeX4 (X = Cl, Br) [BEDT-TTFVO(S) = Bis(ethylenedithio)tetrathiafulvalenoquinone(-thioquinone)-1,3-dithiolemethide]
journal contributionposted on 16.04.2007, 00:00 by Mingxing Wang, Xunwen Xiao, Hideki Fujiwara, Toyonari Sugimoto, Satoru Noguchi, Takekazu Ishida, Takehiko Mori, Hiroko Aruga Katori
By the reaction of new donor molecules, bis(ethylenedithio)tetrathiafulvalenoquinone(-thioquinone)-1,3-dithiolemethides [BEDT-TTFVO (1) and BEDT-TTFVS (2)] with FeX3 (X = Cl, Br) in CS2/CH3CN, 1:1 salts of 1 or 2 with an FeX4- ion (1·FeX4 and 2·FeX4) were obtained as black needle crystals. Their crystal structures are very similar to each other, in which the donor molecules are strongly dimerized and the dimers construct a one-dimensional uniform chain along the a axis, while the FeX4- ions are located at an open space surrounded by the neighboring donor molecules and also construct a one-dimensional uniform chain along the a axis. There are close contacts between the donor molecules and the FeX4- ions and significant differences in the contact distances among the four salts. All of the salts are semiconductors with room-temperature electrical conductivities of 10-4−10-2 S cm-1. The Fe(III) d spins of the FeX4- ions are subject to dominant ferromagnetic interaction through the participation of one of the singlet π spins to form a short-range ferromagnetic d-spin chain. Such neighboring chains interact antiferromagnetically with each other through the singlet π spins and are ordered at 1.0, 2.4, and 0.8 K for 1·FeCl4, 1·FeBr4, and 2·FeCl4, respectively. On the other hand, the antiferromagnetic ordering occurred with some canted angle at 1.9 K to leave a small magnetization for 2·FeBr4.