CoMOF5(pyrazine)(H2O)2(M = Nb, Ta): Two-Layered Cobalt Oxyfluoride Antiferromagnets with Spin Flop Transitions

Two cobalt oxyfluoride antiferromagnets CoMOF5(pyz)(H2O)(2) (M = Nb 1, Ta 2; pyz = pyrazine) have been synthesized via conventional hydrothermal methods and characterized by thermogravimetric (TGA) analysis, FTIR spectroscopy, electron spin resonance (ESR), magnetic susceptibility, and magnetization measurements at both static low field and pulsed high field. The single-crystal X-ray diffraction indicates both compounds 1 and 2 are isostructural and crystallize in the monoclinic space group C2/m with a two-dimensional Co2+ triangular lattice in the ab plane, separated by the nonmagnetic MOF5 (M = Nb 1, Ta 2) octahedra along the c-axis with large intertriangular-lattice Co center dot center dot center dot Co distance. Because of low dimensionality together with frustrated triangular lattice, compounds 1 and 2 exhibit no long-range antiferromagnetic order until similar to 3.7 K. Moreover, a spin flop transition is observed in the magnetization curves at 2 K for both compounds, which is further confirmed by ESR spectra. In addition, the ESR spectra suggest the presence of a zero-field spin gap in both compounds. The high field magnetization measured at 2 K saturates at similar to 7 T with M-s = 1.55 mu(B) for 1 and 1.71 mu(B) for 2, respectively, after subtracting the Van Vleck paramagnetic contribution, which is usually observed for Co2+ ions with pseudospin spin of 1/2 at low temperature. Powder-averaged magnetic anisotropy of g = 3.10 for 1 (3.42 for 2) and magnetic superexchange interaction J/k(B) = -3.2 K for 1 (-3.6 K for 2) are obtained.

Automated summary

Two cobalt oxyfluoride antiferromagnets were synthesized and characterized, showing no long-range antiferromagnetic order until low temperatures due to low dimensionality and frustrated triangular lattice. Spin flop transitions and zero-field spin gaps were observed at low temperatures, with high field magnetization measurements confirming the presence of Co2+ ions with pseudospin spin of 1/2.