Insight into D (6h) Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single‐Ion Magnets

Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph(3)SiO(−) (Ph(3)SiO(−)=anion of triphenylsilanol) and the 2,4‐di‐(t)Bu‐PhO(−) (2,4‐di‐(t)Bu‐PhO(−)=anion of 2,4‐di‐tertbutylphenol) ligands combined with the weak equatorial field of the ligand L(N6), leads to [Dy(III)(L(N6))(2,4‐di‐(t)Bu‐PhO)(2)](PF(6)) (1), [Dy(III)(L(N6))(Ph(3)SiO)(2)](PF(6)) (2) and [Dy(III)(L(N6))(Ph(3)SiO)(2)](BPh(4)) (3) hexagonal bipyramidal dysprosium(III) single‐molecule magnets (SMMs) with high anisotropy barriers of U (eff)=973 K for 1, U (eff)=1080 K for 2 and U (eff)=1124 K for 3 under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher‐order symmetry SMMs.