Rational Electrostatic Design of Easy‐Axis Magnetic Anisotropy in a ZnII–DyIII–ZnII Single‐Molecule Magnet with a High Energy Barrier

Two novel trinuclear complexes ZnCl(μ‐L)Ln(μ‐L)ClZn]ZnCl₃(CH₃OH)]?3 CH₃OH (Ln^III=Dy ( 1 ) and Er ( 2 )) have been prepared from the compartmental ligand N,N′‐dimethyl‐N,N′‐bis(2‐hydroxy‐3‐formyl‐5‐bromo‐benzyl)ethylenediamine (H₂L). X‐ray studies reveal that Ln^III ions are coordinated by two ZnCl(L)]^? units through the phenoxo and aldehyde groups, giving rise to a LnO₈ coordination sphere with square‐antiprism geometry and strong easy‐axis anisotropy of the ground state. Ab initio CASSCF+RASSI calculations carried out on 1 confirm that the ground state is an almost pure M_J=±15/2 Kramers doublet with a marked axial anisotropy, the magnetic moment is roughly collinear with the shortest Dy?O distances. This orientation of the local magnetic moment of the Dy^III ion in 1 is adopted to reduce the electronic repulsion between the oblate electron shape of the M_J=±15/2 Kramers doublet and the phenoxo‐oxygen donor atoms involved in the shortest Dy?O bonds. CASSCF+RASSI calculations also show that the ground and first excited states of the Dy^III ion are separated by 129 cm^?1. As expected for this large energy gap, compound 1 exhibits, in a zero direct‐current field, thermally activated slow relaxation of the magnetization with a large U_eff=140 K. The isostructural Zn–Er–Zn species does not present significant SMM behavior as expected for the prolate electron‐density distribution of the Er^III ion leading to an easy‐plane anisotropy of the ground doublet state.