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Title: Single Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy-Oxide Clusterfullerene Dy2O@C82
Authors: Yang, W.Velkos, G.Liu, F.Sudarkova, S.M.Wang, Y.Zhuang, J.Zhang, H.Li, X.Zhang, X.Büchner, B.Avdoshenko, S.M.Popov, A.A.Chen, N.
Publishers Version:
Issue Date: 2019
Published in: Advanced Science Vol. 6 (2019), No. 20
Publisher: Chichester : John Wiley and Sons Ltd
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; Cages (mine hoists); Crystal symmetry; Dysprosium; Exchange interactions; Excited states; Frequency modulation; Fullerenes; Isomers; Magnetic anisotropy; Magnetic moments; Magnetization; Magnets; Molecules; Oxides; Single crystals; Synthesis (chemical); Antiferromagnetics; Arrhenius behaviors; Magnetization relaxation; Metallofullerenes; Molecular magnetism; Relaxation of magnetization; Single crystal x-ray diffraction; Single-molecule magnet; Dysprosium compounds
DDC: 530
License: CC BY 4.0 Unported
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Appears in Collections:Physik

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