title: Redox Switches for Single-Molecule Magnet Activity: An Ab Initio Insight.
abstract: 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.
authors.affiliation: Theory of Nanomaterials Group, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001, Leuven, Belgium.
authors.forename: Veacheslav
authors.initials: V
authors.lastname: Vieru
authors.affiliation: Theory of Nanomaterials Group, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001, Leuven, Belgium. Liviu.Chibotaru@chem.kuleuven.be.
authors.forename: Liviu F
authors.initials: LF
authors.lastname: Chibotaru
keywords: ab initio calculations; cobalt complex; density functional calculations; single-molecule magnets; unquenched orbital moments