Single Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy‐Oxide Clusterfullerene Dy2O@C82

Abstract

Abstract A new class of single‐molecule magnets (SMMs) based on Dy‐oxide clusterfullerenes is synthesized. Three isomers of Dy2O@C82 with Cs(6), C3v(8), and C2v(9) cage symmetries are characterized by single‐crystal X‐ray diffraction, which shows that the endohedral Dy−(µ2‐O)−Dy cluster has bent shape with very short Dy−O bonds. Dy2O@C82 isomers show SMM behavior with broad magnetic hysteresis, but the temperature and magnetization relaxation depend strongly on the fullerene cage. The short Dy−O distances and the large negative charge of the oxide ion in Dy2O@C82 result in the very strong magnetic anisotropy of Dy ions. Their magnetic moments are aligned along the Dy−O bonds and are antiferromagnetically (AFM) coupled. At low temperatures, relaxation of magnetization in Dy2O@C82 proceeds via the ferromagnetically (FM)‐coupled excited state, giving Arrhenius behavior with the effective barriers equal to the AFM‐FM energy difference. The AFM‐FM energy differences of 5.4–12.9 cm−1 in Dy2O@C82 are considerably larger than in SMMs with {Dy2O2} bridges, and the Dy∙∙∙Dy exchange coupling in Dy2O@C82 is the strongest among all dinuclear Dy SMMs with diamagnetic bridges. Dy‐oxide clusterfullerenes provide a playground for the further tuning of molecular magnetism via variation of the size and shape of the fullerene cage.

Keywords

• antiferromagnetic
• dysprosium
• exchange interactions
• metallofullerene
• oxide
• single molecule magnets