Approaches to Molecular Magnetic Materials from the Use of Cyanate Groups in Higher Oxidation State Metal Cluster Chemistry: Mn14 and Mn16

The initial employment of cyanato groups in higher oxidation state manganese cluster chemistry, in conjunction with the gem-diolate form of di-2-pyridylketone or 2,6-diacetylpyridine dioxime chelate ligands, has afforded structurally interesting MnII/III14 and MnII/III/IV16 clusters, respectively. In both complexes, the end-on bridging cyanato groups show an obvious preference in binding through their O atom, a significantly different ligation than that for the homoatomic-type N3 ligand. The Mn14 compound shows entirely visible out-of-phase signals below 5 K and large hysteresis loops below 2 K.