Ferromagnetic exchange in a twisted, oxime-bridged [mniii2] dimer
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2012-01-01Author
Houton, Edel
Taylor, Stephanie M.
Beedle, Christopher C.
Cano, Joan
Piligkos, Stergios
Hill, Stephen
Ryder, Alan G.
Brechin, Euan K.
Jones, Leigh F.
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Houton, Edel; Taylor, Stephanie M. Beedle, Christopher C.; Cano, Joan; Piligkos, Stergios; Hill, Stephen; Ryder, Alan G.; Brechin, Euan K.; Jones, Leigh F. (2012). Ferromagnetic exchange in a twisted, oxime-bridged [mniii2] dimer. Dalton Transactions 41 (27), 8340-8347
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Abstract
The dimeric complex [Mn-2(III)(Naphth-sao)(2)(Naphth-saoH)(2)(MeOH)(2)]center dot 4MeOH (1.4MeOH), acts as a simple model complex with which to examine the magneto-structural relationship in polymetallic, oxime-bridged Mn-III complexes. Dc magnetic susceptibility studies reveal that ferromagnetic exchange is mediated through the heavily twisted Mn-O-N-Mn moiety (J = + 1.24 cm(-1)) with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D-(MnIII) = -3.94 cm(-1). Theoretical studies on simplified model complexes of 1 reveal that calculated values of the exchange coupling and the anisotropy are in excellent agreement with experiment, with the weak ferromagnetism resulting from an accidental orthogonality between the Mn-N-O plane of the first MnIII ion and the Jahn-Teller axis of the second Mn-III ion.