Disorder, exchange and magnetic anisotropy in the room-temperature molecular magnet V[TCNE]x – A theoretical study

Abstract We report quantum chemical calculations to address yet unresolved and puzzling questions regarding the structural and magnetic disorder of V[TCNE] x (TCNE = tetracyanoethylene, x ∼ 2), the first room-temperature molecule-based magnet. Starting from an ideal lattice model, containing TCNE ligands either tetra- or bi-connected to vanadium(II) ions, we identify the key sources of structural disorder, explaining the amorphousness and non-stoichiometric nature of V[TCNE] x . The proposed model is prone to static disorder in terms of the bulk distribution of the tetra-connected TCNE species and to dynamic effects due to the relative rotational freedom of the bi-connected TCNE moieties. Density functional theory (DFT) calculations of the model system with rotated TCNE molecules show a rough energy landscape, consistent with the presence of magnetic irreversibilities in the system. The broken symmetry DFT approach evidences ferrimagnetic spin orientation for all TCNE configurations, ruling out the spin glass model. Multiconfigurational calculations with additional spin–orbit interaction allow for the account of the single-ion-anisotropy of the V(II) ions in different environments. We determine a small uniform zero-field-splitting ( D c = −0.03 K) of the bulk as well as a sizeable random anisotropy ( D r = 0.56 K) due to TCNE vacancies. We clarify the interplay of ferrimagnetism and random magnetic anisotropy in this system, which favours correlated sperimagnetic and not spin glass behaviour, in agreement with puzzling experimental data. Our approach goes beyond the material of interest here, as it can be applied to other disordered molecular magnets by correlating the sources of disorder with their effects on the magnetic properties.