Zl. Huang et al., Ab-initio XRPD crystal structure and giant hysteretic effect (H-c=5.9 T) of a new hybrid terephthalate-based cobalt(II) magnet, CHEM MATER, 12(9), 2000, pp. 2805-2812
A new terephthalate-based cobalt hydroxide, Co-2(OH)(2)(C8H4O4), was synthe
sized by the hydrothermal method. Its crystal structure has been determined
by ab-initio XRPD methods (monoclinic, C2/m, a = 19.943(1), b = 3.2895(1),
c = 6.2896(3) Angstrom, beta = 95.746(3)degrees) and fully refined by the
Rietveld technique down to R-p = 0.15 for 9301 observed data (178 independe
nt reflections). The terephthalates are coordinated and pillared directly t
o the cobalt hydroxide layers and thus a three-dimensional framework is for
med. Because of the bonds with the terephthalates, two crystallographically
inequivalent cobalt sites are found inside the hydroxide layers, with diff
erent octahedral orientations. Magnetic studies show that the intralayer ex
change interaction between Co(II) ions is ferromagnetic but the whole syste
m orders antiferromagnetically at 48 K with a metamagnetic transition above
a threshold field of 0.2 T. The existence of conjugated pi electrons in te
rephthalates explains the antiferromagnetic interactions between the layers
. Below 45 K, the compound exhibits a hysteretic metamagnetic loop and a re
mnant moment that is small down to about 30 K, and then rises suddenly reac
hing a plateau below 15 K. However, at low temperatures the remnant moment
is still only a fraction of the full Co(II) moment, which is a sign of cant
ed antiferromagnetism associated with a non-collinear orientation of the mo
ments between the layers. The magnetization loop shows a giant coercive fie
ld of 5.9 T at 4.2 K, which must be related to an extremely large single-io
n anisotropy on the Co sites.