Magnetic Properties of Metal⁻Organic Coordination Networks Based on 3d Transition Metal Atoms.

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal⁻organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1:1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni⁻TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn⁻TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin⁻orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni⁻TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.