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

The synthesis and characterisation of a large family of hexametallic [Mn-6(III)] Single-Molecule Magnets of general formula [(Mn6O2)-O-III(R-sao)(6)(X)(2)(Sol)(4-6)] (where R = H, Me, Et; X = -O2CR'(R' = H, Me, Ph etc) or Hal(-); sol = EtOH, MeOH and/or H2O) are presented. We show how deliberate structural distortions of the [Mn3O] 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.