Boosting the mono-axial crystal field in stable high-coordinate Dy(III) single-ion magnets by substitution of the phenoxy axial ligand

Synthesis of air-stable and high-performance single-molecule magnets (SMMs) is challenging. Here, a heptadentate pentapyridyldiamine (BPA-TPA) ligand and fine-tuned axial phenoxy ligands are used to synthesize two triangular dodecahedral Dy(III) complexes [Dy(BPA-TPA)(4-methoxy-PhO)](BPh4)(2)center dot 3CH(2)Cl(2) (4) and [Dy(BPA-TPA)(2,4-dimethyl-PhO)](BPh4)(2)center dot 0.85CH(2)Cl(2) (5). Both complexes have high effective barriers exceeding 400 K and magnetic hysteresis up to 8 K, which is ascribed to one strong and short Dy-O bond combined with seven weak Dy-N bonds. Ab initio calculations reveal the thermally activated quantum tunneling of magnetization through the first excited Kramers doublet, due to the presence of a strong axial Dy-O crystal ligand. Substitution of the phenoxy ligand leads to more constrained vibrations, improving the magnetic hysteresis behavior for 5.