1-D coordination polymers consisting of a high-spin Mn17 octahedral unit

The reaction of [Mn(O2CMe)2] · 4H2O with pdH2 (1,3-propanediol) or mpdH2 (2-methyl-1,3-propanediol) in the presence of NaN3 in MeCN/py (py = pyridine) results in the formation of two new one-dimensional coordination polymers composed of a [MnIII6MnII11(μ4-O)8(μ3-N3)4]25+ octahedral unit. The peripheral ligation is completed by pd2− (or mpd2−), acetate, pyridine and μ-1,3-N3− ligands. The latter bridges each Mn17 unit to its neighboring one, resulting in the formation of the two 1-D coordination polymers. Variable-temperature dc magnetic susceptibility studies indicate the existence of predominantly ferromagnetic interactions and a resulting giant ground state spin within the Mn17 units and intermolecular antiferromagnetic exchange interactions between the neighboring Mn17 units that result in diamagnetic ground spin states for both polymeric compounds.

The use of the combination of pdH2 or mpdH2 and N3− ligands in reactions with MnII carboxylate salts resulted in two one-dimensional coordination polymers [(1)∞ and (2)∞] (figure; color scheme: Mn, blue; O, red; N, green; C, grey) consisting of a [MnIII11MnII6(μ4-Ο)8(μ3-N3)4]25+ octahedral unit. The Mn17 unit seems to have a giant spin ground state (S); however, both polymers display S ≈ 0 spin ground states due to intermolecular antiferromagnetic interactions between the neighboring Mn17 units.Figure optionsDownload as PowerPoint slide