What controls the magnetic interaction in bis-μ-alkoxo mniii dimers? a combined experimental and theoretical exploration
Berg, Nelly Rajeshkumar, Thayalan Taylor, Stephanie M. Brechin, Euan K. Rajaraman, Gopalan Jones, Leigh F.
Berg, Nelly
Rajeshkumar, Thayalan
Taylor, Stephanie M.
Brechin, Euan K.
Rajaraman, Gopalan
Jones, Leigh F.
Publication Date
2012-03-29
Keywords
coordination complexes, density functional calculations, magneto-structural correlations, manganese, molecular magnetism, binuclear manganese(iii) complex, transition-metal-complexes, single-molecule magnets, spin ground-state, exchange coupling-constants, catalase-like activity, schiff-base complex, gaussian-basis sets, magnetostructural correlations, crystal-structure
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Article
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Berg, Nelly; Rajeshkumar, Thayalan; Taylor, Stephanie M. Brechin, Euan K.; Rajaraman, Gopalan; Jones, Leigh F. (2012). What controls the magnetic interaction in bis-μ-alkoxo mniii dimers? a combined experimental and theoretical exploration. Chemistry - A European Journal 18 (19), 5906-5918
Abstract
The synthesis and magnetic characterisation of a series of bis-mu-alkoxide bridged MnIII dinuclear complexes of general formula [MnIII2(mu-OR)2(biphen)2(ROH)x(L)y] (where R=Me, Et; H2biphen=2,2'-biphenol and L=terminally bonded N-donor ligand) is described, doubling the literature basis set for this type of complex. Building on these findings we have categorised all known mu-OR bridged MnIII dinuclear complexes into one of three classifications with respect to their molecular structures. We have then employed DFT and MO calculations to assess all potential magneto-structural correlations for this class of compound in order to identify the structural requirements for constructing ferromagnetic family members. Our analysis indicates that the most influential parameter which governs the exchange interaction in this class of compounds is the relative orientation of the JT axes of the MnIII atoms. A perpendicular orientation of the JT axes leads to a large ferromagnetic contribution to the exchange. These results also suggest that a large ferromagnetic interaction and a large anisotropy are unlikely to co-exist in such structural types.
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Wiley-Blackwell
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Attribution-NonCommercial-NoDerivs 3.0 Ireland