Pressure effect on bulk weak ferromagnets: (BDH-TTP)[M(isoq)2(NCS)4] (M = Cr(III), Fe(III); isoq = Isoquinoline).
The pressure dependence of the magnetic properties of weak ferromagnets (BDH-TTP)[M(isoq)2(NCS)4] [BDH-TTP = 2,5-bis(1',3'-dithiolan-2'-ylidene)-1,3,4,6-tetrathiapentalene; M = Cr, Fe; isoq = isoquinoline] is discussed. These salts form two-dimensional magnetic sheets, where ferrimagnetic chains of donor cation radical (S = 1/2) and anion [S = 3/2 (Cr), 5/2 (Fe)] are antiferromagnetically connected by weak donor-donor and anion-anion interchain S...S contacts. Under ambient pressure, both the Cr and Fe salts undergo a weak ferromagnetic transition at Tc = 7.6 K, below which a spontaneous magnetization emerges along the direction perpendicular to the sheets. The application of the pressure elevates the transition temperatures up to 16.6 and 11.6 K at 9 kbar for M = Cr and Fe, respectively. As the pressure increases, the remanent magnetization M(r) decreases, whose pressure dependence for the Cr salt is larger than that for the Fe salt. This difference indicates that the spin-canting angle of the Cr salt is reduced because of the increase of antiferromagnetic interaction by applied pressure, in contrast to the Fe salt, where single-ion anisotropy contributes less. The quantitative analysis of the magnetization curves of the Cr salt using the mean-field approximation reveals that the intermolecular exchange interaction increases as the pressure increases, among which the interchain anion-anion interaction has the highest pressure sensitivity. This result is consistent with the temperature dependence of the crystal structure showing that the thermal contraction in the distances of interchain anion-anion S...S contacts is the most remarkable in intrachain S...S contacts. The large pressure dependence of the transition temperature of these salts is therefore explained as a result of the fact that the interchain interactions, the anion-anion interaction in particular, are strengthened by applied pressure.
Kudo
Satoshi
S
Department of Chemistry, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
Miyazaki
Akira
A
Enoki
Toshiaki
T
Golhen
Stéphane
S
Ouahab
Lahcène
L
Toita
Takashi
T
Yamada
Jun-Ichi
J