Single-Molecule Magnets: Preparation and Properties of Low Symmetry [Mn₄O₃(O₂CPh-R)₄(dbm)₃] Complexes with S = ⁹/₂

The preparation and properties of [Mn4O3(O2CPh-R)4(dbm)3] (R = H, p-Me, p-OMe, and o-Cl; dbm- is the anion of dibenzoylmethane) single-molecule magnets (SMMs) with virtual CS symmetry are reported. They were prepared by controlled potential electrolysis in 26−80% yields. The structures comprise a distorted-cubane core of virtual CS symmetry, in contrast to the other, more common complexes of this type with virtual C3V symmetry. Solid-state magnetic susceptibility data establish the complexes have S = 9/2 ground-state spins, and ac susceptibility studies indicate they are single-molecule magnets (SMMs). Magnetization vs dc field sweeps below 1.00 K reveal hysteresis loops confirming a SMM, with a very large step at zero applied field diagnostic of fast quantum tunneling of magnetization (QTM) through the anisotropy barrier. The fast QTM rate suggested a significant rhombic ZFS parameter E, as expected from the low (virtual CS) symmetry. This was confirmed by high-frequency electron paramagnetic resonance spectroscopy on polycrystalline and single-crystal studies. The results confirm the importance of symmetry on the QTM rates.