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Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal–metal bond

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical...

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Detalles Bibliográficos
Autores principales: Liu, Fupin, Velkos, Georgios, Krylov, Denis S., Spree, Lukas, Zalibera, Michal, Ray, Rajyavardhan, Samoylova, Nataliya A., Chen, Chia-Hsiang, Rosenkranz, Marco, Schiemenz, Sandra, Ziegs, Frank, Nenkov, Konstantin, Kostanyan, Aram, Greber, Thomas, Wolter, Anja U. B., Richter, Manuel, Büchner, Bernd, Avdoshenko, Stanislav M., Popov, Alexey A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6362165/
https://www.ncbi.nlm.nih.gov/pubmed/30718550
http://dx.doi.org/10.1038/s41467-019-08513-6
Descripción
Sumario:Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln(2)@C(80)(CH(2)Ph) dimetallofullerenes (Ln(2) = Y(2), Gd(2), Tb(2), Dy(2), Ho(2), Er(2), TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal–metal bonding orbital. Tb(2)@C(80)(CH(2)Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln(2)@C(80)(CH(2)Ph) is redox active, enabling electrochemical tuning of the magnetism.