Rare earth metal compounds containing soft heteroatom donor ligands have attracted considerable interest in recent years. The combination of M<sup>3+</sup> cations with heavy p-block donor atoms results in a so-called hard-soft 'mismatch' that can lead to unusual bonding properties and to distinct reactivity. Within this context, rare earth complexes of anionic phosphorus donor ligands have been extensively studied. Some analogous chemistry with anionic arsenic ligands is known, but such compounds are still very rare. The use of P- and As-donor ligands in the design of lanthanide single-molecule magnets (SMMs) is, however, entirely unknown. In this lecture, the dynamic magnetic properties of a series of dysprosium complexes with phosphide, phosphinidene, arsenide and arsinidene ligands will be described. The experimental studies are complemented by ab initio calculations, which have enabled us to construct a model for the magnetic anisotropy and magnetization relaxation mechanisms in our SMMs. The theoretical model also provides insight into how SMMs with larger anisotropy barriers may be designed, and selected new systems will also be presented.

Phosphorus- and arsenic-ligated lanthanide single-molecule magnets

249th National Meeting (2015)

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