Accidentally on purpose: construction of a ferromagnetic, oxime-based [MnIII2] dimer

TY - JOUR

T1 - Accidentally on purpose: construction of a ferromagnetic, oxime-based [MnIII2] dimer

AU - Inglis, Ross

AU - Houton, Edel

AU - Liu, Junjie

AU - Prescimone, Alessandro

AU - Cano, Joan

AU - Piligkos, Stergios

AU - Hill, Stephen

AU - Jones, Leigh F.

AU - Brechin, Euan K.

PY - 2011/10/21

Y1 - 2011/10/21

N2 - The serendipitous self-assembly of the complex [MnIII 2ZnII2(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 [MnIII3] and [MnIII6] clusters.

AB - The serendipitous self-assembly of the complex [MnIII 2ZnII2(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 [MnIII3] and [MnIII6] clusters.

M3 - Journal article

SN - 1477-9226

VL - 40

SP - 9999

EP - 10006

JO - Dalton Transactions

JF - Dalton Transactions

ER -