Attempting to understand (and control) the relationship between structure and magnetism in an extended family of Mn6 single-molecule magnets

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Abstract

The synthesis and characterisation of a large family of hexametallic [Mn(III)(6)] Single-Molecule Magnets of general formula [Mn(III)(6)O(2)(R-sao)(6)(X)(2)(sol)(4-6)] (where R = H, Me, Et; X = (-)O(2)CR' (R' = H, Me, Ph etc) or Hal(-); sol = EtOH, MeOH and/or H(2)O) are presented. We show how deliberate structural distortions of the [Mn(3)O] trinuclear moieties within the [Mn(6)] complexes are used to tune their magnetic properties. These findings highlight a qualitative magneto-structural correlation whereby the type (anti- or ferromagnetic) of each Mn(2) pairwise magnetic exchange is dominated by the magnitude of each individual Mn-N-O-Mn torsion angle. The observation of magneto-structural correlations on such large polymetallic complexes is rare and represents one of the largest studies of this kind.

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