期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 22, 期 15, 页码 5309-5318出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201504490
关键词
ab initio calculations; density functional calculations; cobalt complex; single-molecule magnets; unquenched orbital moments
资金
- Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)
- GOA program at the KU Leuven
- INPAC program at the KU Leuven
- Methusalem program at the KU Leuven
A dinuclear Co-II complex (1) featuring unprecedented anodic and cathodic switches for single-molecule magnet (SMM) activity has been recently investigated (J. Am. Chem. Soc. 2013, 135, 14670). The presence of sandwiched radicals in different oxidation states of this compound mediates magnetic coupling between the high-spin (S=3/2) cobalt ions, which gives rise to SMM activity in both the oxidized ([1(OEt2)](+)) and reduced ([1](-)) states. This feature represents the first example of a SMM exhibiting fully reversible, dual ON/OFF switchability. Here we apply ab initio and broken-symmetry DFT calculations to elucidate the mechanisms responsible for magnetic properties and magnetization blocking in these compounds. It is found that due to the strong delocalization of the magnetic molecular orbital, there is a strong antiferromagnetic interaction between the radical and cobalt ions. The lack of high axiality of the cobalt centres explains why these compounds possess slow relaxation of magnetization only in an applied dc magnetic field.
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