Single Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy‐Oxide Clusterfullerene Dy(2)O@C(82)

A new class of single‐molecule magnets (SMMs) based on Dy‐oxide clusterfullerenes is synthesized. Three isomers of Dy(2)O@C(82) with C (s)(6), C (3v)(8), and C (2v)(9) cage symmetries are characterized by single‐crystal X‐ray diffraction, which shows that the endohedral Dy−(µ(2)‐O)−Dy cluster has bent shape with very short Dy−O bonds. Dy(2)O@C(82) 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 Dy(2)O@C(82) 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 Dy(2)O@C(82) 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 Dy(2)O@C(82) are considerably larger than in SMMs with {Dy(2)O(2)} bridges, and the Dy∙∙∙Dy exchange coupling in Dy(2)O@C(82) 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.