Twisting, bending, stretching: strategies for making ferromagnetic [Mn(III)3] triangles.

The synthesis and characterisation of a large family of trimetallic [Mn(III)(3)] Single-Molecule Magnets is presented. The complexes reported can be divided into three categories with general formulae (type 1) [Mn(III)(3)O(R-sao)(3)(X)(sol)(3-4)] (where R = H, Me, (t)Bu; X = (-)O(2)CR (R = H, Me, Ph etc); sol = py and/or H(2)O), (type 2) [Mn(III)(3)O(R-sao)(3)(X)(sol)(3-5)] (where R = Me, Et, Ph, (t)Bu; X = (-)O(2)CR (R = H, Me, Ph etc); sol = MeOH, EtOH and/or H(2)O), and (type 3) [Mn(III)(3)O(R-sao)(3)(sol)(3)(XO(4))] (where R = H, Et, Ph, naphth; sol = py, MeOH, beta-pic, Et-py, (t)Bu-py; X = Cl, Re). We show that deliberate structural distortions of the molecule can be used to tune the observed magnetic properties. In the crystals the ferromagnetic triangles are involved in extensive inter-molecular H-bonding which is clearly manifested in the magnetic behaviour, producing exchange-biased SMMs. These interactions can be removed by ligand replacement to give "simpler" SMMs.