Synthesis, crystal structures and magnetic properties of a family of manganese phosphonate clusters with diverse structures†
Abstract
Four novel manganese phosphonate clusters, namely Cl@[Mn6(t-BuPO3)8(H2O)2(CH3OH)4][OH] (1), Br@[Mn6(t-BuPO3)8(H2O)2(CH3OH)4][OH]·4H2O (2), [Mn13O6(t-BuPO3)10(OH)6(CH3OH)6][Mn13O6(t-BuPO3)10(OCH3)6(t-BuPO3H2)2(H2O)4]·2CH3OH·10H2O (3) and [Mn15K2O8(t-BuPO3)10(CH3O)4(C6H5COO)4(H2O)8]·6H2O (4), have been successfully synthesized in the presence of tert-butylphosphonic acid, carboxylic acid, NBun4MnO4 and different manganese sources. These clusters were characterized by elemental analyses, IR spectroscopy, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Single-crystal structure analyses reveal that the structures of 1–4 are diverse. The structure of cluster 1 is analogous to that of cluster 2, which displays a cage-like arrangement with one halide ion (Cl−, Br−) lying inside the centre of the cave. Cluster 3 is a carboxylate-free manganese phosphonate cluster consisting of two similar Mn13 structural units. Moreover, there exist two potassium ions and fifteen manganese ions in the heterometallic cluster 4. In addition, solid-state DC magnetic susceptibility measurements indicate the existence of overall antiferromagnetic (AF) exchange interactions between the Mn ions in all clusters.
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