Accidentally on purpose: construction of a ferromagnetic, oxime-based [Mn(III)2] dimer |
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Authors: | Inglis Ross Houton Edel Liu Junjie Prescimone Alessandro Cano Joan Piligkos Stergios Hill Stephen Jones Leigh F Brechin Euan K |
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Institution: | EaStCHEM School of Chemistry, The University of Edinburgh, The Kings Buildings, West Mains Road, Edinburgh, UK EH9 3JJ. |
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Abstract: | The serendipitous self-assembly of the complex Mn(III)(2)Zn(II)(2)(Ph-sao)(2)(Ph-saoH)(4)(hmp)(2)] (1),whose magnetic core consists solely of two symmetry equivalent Mn(iii) ions linked by two symmetry equivalent -N-O- moieties, provides a relatively simple model complex with which to study the magneto-structural relationship in oxime-bridged Mn(III) cluster compounds. Dc magnetic susceptibility measurements reveal ferromagnetic (J = +2.2 cm(-1)) exchange resulting in an S = 4 ground state. Magnetisation measurements performed at low temperatures and high fields reveal the presence of significant anisotropy, with ac measurements confirming slow relaxation of the magnetisation and Single-Molecule Magnetism behaviour. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D((Mn(III))) = -3.83 cm(-1). DFT studies on a simplified model complex of 1 reveal a pronounced dependence of the exchange coupling on the relative twisting of the oxime moiety with respect to the metal ion positions, as suggested previously in more complicated Mn(III)(3)] and Mn(III)(6)] clusters. |
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