How to Build Molecules with Large Magnetic Anisotropy

Predicting single‐molecule magnets? Magnetic anisotropy, a property that plays a key role in single‐molecule magnets (SMMs), has been analyzed by using theoretical methods. Mononuclear complexes and the dependence of the magnetic anisotropy on their geometrical and electronic structure, as well as how such mononuclear complexes must be combined as building blocks to obtain polynuclear complexes with large anisotropy (see figure) are considered. magnified image The magnetic anisotropy of mononuclear transition‐metal complexes has been studied by means of electronic structure calculations based on density functional theory. The variation of the zero‐field splitting (ZFS) parameters has been analyzed for the following characteristic distortions: a tetragonal Jahn–Teller distortion, the Bailar twist, the Berry pseudorotation, and the planarization of tetrahedral complexes. Finally, the coupling of mononuclear building blocks in polynuclear complexes to obtain a large negative magnetic anisotropy necessary to improve their single‐molecule‐magnet (SMM) behavior has been studied.