Single Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy-Oxide Clusterfullerene Dy2O@C82
Wei Yang1, Georgios Velkos2, Fupin Liu*2, Svetlana M. Sudarkova2, Yaofeng Wang1, Jiaxin Zhuang1, Hanning Zhang1, Xiang Li1, Xingxing Zhang1, Bernd Büchner2, Stanislav M. Avdoshenko*2, Alexey A. Popov*2, and Ning Chen*1（谌宁）
1 College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou, Jiangsu 215123, P. R. China
2 Leibniz Institute for Solid State and Materials Research (IFW Dresden) Helmholtzstrasse 20, 01069 Dresden, Germany
Adv. Sci. 2019, 6, 1901352
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.
链接：https://onlinelibrary.wiley.com/doi/full/10.1002/advs.201901352