Accidentally on purpose: construction of a ferromagnetic, oxime-based [Mn-2(III)] dimer

Ross Inglis, Edel Houton, Junjie Liu, Alessandro Prescimone, Joan Cano, Stergios Piligkos, Euan K. Brechin, Stephen Hill

Research output: Contribution to journalArticlepeer-review

Abstract

The serendipitous self-assembly of the complex [(Mn2Zn2II)-Zn-III(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-(MnIII) = -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-3(III)] and [Mn-6(III)] clusters.

Original languageEnglish
Pages (from-to)9999-10006
Number of pages8
JournalDalton Transactions
Volume40
Issue number39
DOIs
Publication statusPublished - 2011

Keywords

  • TRANSITION-METAL-COMPLEXES
  • SINGLE-MOLECULE MAGNETS
  • EXCHANGE COUPLING-CONSTANTS
  • LOW-DIMENSIONAL CONDUCTORS
  • GAUSSIAN-BASIS SETS
  • MAGNETOSTRUCTURAL CORRELATIONS
  • POLYNUCLEAR COMPLEXES
  • ATOMS LI
  • DENSITY
  • SUSCEPTIBILITY

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