Understanding Single-Molecule Magnet properties of lanthanide complexes from 4f orbital splitting

Abstract

We present an approach for connecting the magnetic anisotropy of lanthanide mononuclear complexes with their f-orbital splitting for both idealized and real coordination environments. Our proposal is straightforward to apply and provides sensible estimations of the energy spacing of the ground multiplet for axial magnetic systems. This energy splitting controls Single-Molecule Magnet properties of lanthanide complexes, determining key parameters such as the demagnetization energy barrier (U_eff). Importantly, this approach is consistent with the current paradigm of oblate and prolate preferences for the distribution of the f-electron density, but delivers a finer description for ions belonging to the same group (e.g. the oblates Tb^III and Dy^III). The model provides simple explanations for some general trends observed experimentally (e.g. the low barriers for Er^III complexes in comparison to Dy^III or the large barriers observed for cyclopentadienyl Dy^III complexes in comparison with other ligands based on organometallic rings), contributing as a valuable tool to expand our description of ligand field effects in lanthanide-based SMMs.