Magneto-structural studies of two M–O–M bridged homochiral mixed valence Co(II)/Co(III) complexes

Two mixed-valence cobalt complexes, [CoIICoIII2(mpm)6](ClO4)2 (1) and [CoII2CoIII2(μ3-OMe)2(μ-mpm)4(NO3)4] (2), where mpm is the deprotonated form of R or S α-methyl-2-pyridinemethanol, have been structurally and magnetically characterized. Both complexes crystallize in chiral space groups, where 1 is a trinuclear compound with a linear Co(III)–Co(II)–Co(III) topology and 2 is a tetranuclear cluster with a defect dicubane-type structure that has two missing vertices. In both cases the mpm− ligand bridges adjacent Co ions in a η1:η2:μ manner. The molecular geometries of the complexes reveal the Co ions are octahedral, where the greatest deviation from Oh symmetry is apparent for the HS d7 Co(II) ions. The chirality of 1 and 2 were studied by circular dichroism spectroscopy where opposite Cotton effects are observed for the R- and S-enantiomers of both complexes. Magnetic susceptibility studies reveal the presence of largely quenched first order orbital angular momentum together with weak ion or intermolecular dipole exchange.