New Synthetic Route toward Heterometallic 3d–3d′ and 3d–4f Single-Molecule Magnets. The First Co^II–Mn^III Heterometallic Complex

Abstract

Four tetranuclear heterometallic complexes, [Co^II₂Mn₂^III(dpm)₄(MeO)₆] (<b>1</b>) and [Ln^III₂­Mn^III₂­(dpm)₆­(MeO)₆(MeOH)_<i>n</i>], where Ln = Gd (<b>2</b>, <i>n</i> = 2), Tb (<b>3</b>, <i>n</i> = 2), and Dy (<b>4</b>, <i>n</i> = 0), have been obtained following the same general synthetic route, namely, the one-pot reaction between 2,2,6,6-tetrametil-3,5-heptanodione (Hdpm), MnCl₂ and CoCl₂ or Ln­(NO₃)₃ in the presence of sodium methoxide. Within the four compounds, the metal ions bridged by methoxide ligands display a defect-diheterocubane core. Compounds <b>1</b>, <b>3</b>, and <b>4</b> show slow relaxation of the magnetization below 4 K