ABSTRACT
A comprehensive understanding of the ligand field and its influence on the degeneracy and population of d-orbitals in a specific coordination environment are crucial for the rational design and enhancement of magnetic anisotropy of single-ion magnets (SIMs). Herein, we report the synthesis and comprehensive magnetic characterization of a highly anisotropic CoII SIM, [L2Co](TBA)2 (L is an N,N'-chelating oxanilido ligand), that is stable under ambient conditions. Dynamic magnetization measurements show that this SIM exhibits a large energy barrier to spin reversal U eff > 300 K and magnetic blocking up to 3.5 K, and the property is retained in a frozen solution. Low-temperature single-crystal synchrotron X-ray diffraction used to determine the experimental electron density gave access to Co d-orbital populations and a derived U eff, 261 cm-1, when the coupling between the d x 2 - y 2 and dxy orbitals is taken into account, in very good agreement with ab initio calculations and superconducting quantum interference device results. Powder and single-crystal polarized neutron diffraction (PNPD, PND) have been used to quantify the magnetic anisotropy via the atomic susceptibility tensor, revealing that the easy axis of magnetization is pointing along the N-Co-N' bisectors of the N,N'-chelating ligands (3.4° offset), close to the molecular axis, in good agreement with complete active space self-consistent field/N-electron valence perturbation theory to second order ab initio calculations. This study provides benchmarking for two methods, PNPD and single-crystal PND, on the same 3d SIM, and key benchmarking for current theoretical methods to determine local magnetic anisotropy parameters.
ABSTRACT
It is noteworthy that chemical substitution of BaFe2As2 (122) with the noble elements Cu and Au gives superconductivity with a maximum T c ≈ 3 K, while Ag substitution (Ag-122) stays antiferromagnetic. For Ba(Fe1-x TM x )2As2, TM = Cu, Au, or Ag, and by doping an amount of x = 0.04, a-lattice parameter slightly increases (0.4%) for all TM dopants, while c-lattice decreases (-0.2%) for TM = Cu, barely moves (0.05%) for Au, and increases (0.2%) for Ag. Despite the naive expectation that the noble elements of group 11 should affect the quantum properties of 122 similarly, they produce significant differences extending to the character of the ground state. For the Ag-122 crystal, evidence of only a filamentary superconductivity is noted with pressure. However, for Au and Cu doping (x ≈ 0.03) we find a substantial improvement in the superconductivity, with T c increasing to 7 K and 7.5 K, respectively, under 20 kbar of pressure. As with the ambient pressure results, the identity of the dopant therefore has a substantial impact on the ground state properties. Density functional theory calculations corroborate these results and find evidence of strong electronic scattering for Au and Ag dopants, while Cu is comparatively less disruptive to the 122 electronic structure.
ABSTRACT
Within the BaFe2As2 crystal lattice, we partially substitute thallium for barium and report the effects of interlayer coupling in Ba(1-x)Tl(x)Fe2As2 crystals. We demonstrate the unusual effects of magneto-elastic coupling and charge doping in this iron-arsenide material, whereby Néel temperature rises with small x, and then falls with additional x. Specifically, we find that Néel and structural transitions in BaFe2As2 (T(N) = T(s) = 133 K) increase for x = 0.05 (T(N) = 138 K, T(s) = 140 K) from magnetization, heat capacity, resistivity, and neutron diffraction measurements. Evidence from single crystal X-ray diffraction and first principles calculations attributes the stronger magnetism in x = 0.05 to magneto-elastic coupling related to the shorter intraplanar Fe-Fe bond distance. With further thallium substitution, the transition temperatures decrease for x = 0.09 (T(N) = T(s) = 131 K), and this is due to charge doping. We illustrate that small changes related to 3d transition-metal state can have profound effects on magnetism.
