title: Accidentally on purpose: construction of a ferromagnetic, oxime-based [Mn(III)2] dimer.
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.
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, The Kings Buildings, West Mains Road, Edinburgh, UK EH9 3JJ.
authors.forename: Ross
authors.initials: R
authors.lastname: Inglis
authors.forename: Edel
authors.initials: E
authors.lastname: Houton
authors.forename: Junjie
authors.initials: J
authors.lastname: Liu
authors.forename: Alessandro
authors.initials: A
authors.lastname: Prescimone
authors.forename: Joan
authors.initials: J
authors.lastname: Cano
authors.forename: Stergios
authors.initials: S
authors.lastname: Piligkos
authors.forename: Stephen
authors.initials: S
authors.lastname: Hill
authors.forename: Leigh F
authors.initials: LF
authors.lastname: Jones
authors.forename: Euan K
authors.initials: EK
authors.lastname: Brechin