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

被引:126
|
作者
Liu, Fupin [1 ]
Velkos, Georgios [1 ]
Krylov, Denis S. [1 ]
Spree, Lukas [1 ]
Zalibera, Michal [2 ]
Ray, Rajyavardhan [1 ,3 ]
Samoylova, Nataliya A. [1 ]
Chen, Chia-Hsiang [1 ]
Rosenkranz, Marco [1 ]
Schiemenz, Sandra [1 ]
Ziegs, Frank [1 ]
Nenkov, Konstantin [1 ]
Kostanyan, Aram [4 ]
Greber, Thomas [4 ]
Wolter, Anja U. B. [1 ]
Richter, Manuel [1 ,3 ]
Buechner, Bernd [1 ]
Avdoshenko, Stanislav M. [1 ]
Popov, Alexey A. [1 ]
机构
[1] Leibniz Inst Solid State & Mat Res IFW Dresden, Helmholtzstr 20, D-01069 Dresden, Germany
[2] Slovak Univ Technol Bratislava, Inst Phys Chem & Chem Phys, Radlinskeho 9, Bratislava 81237, Slovakia
[3] Tech Univ Dresden, Dresden Ctr Computat Mat Sci DCMS, D-01062 Dresden, Germany
[4] Phys Inst Univ Zurich, Winterthurerstr 190, CH-8057 Zurich, Switzerland
基金
欧盟地平线“2020”; 瑞士国家科学基金会;
关键词
EXCHANGE INTERACTION; MAGNETIC BLOCKING; AB-INITIO; SINGLE; ION; BARRIER; METALLOFULLERENES; GD-2-AT-C79N; RELAXATION; BEHAVIOR;
D O I
10.1038/s41467-019-08513-6
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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(CH2Ph) 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(CH2Ph) 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(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.
引用
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页数:11
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