Synthesis, structure and magnetism of the mixed-valent phosphonate cage, [MnIIMnIII12(μ4-O)6(μ-OH)6(O3P–t-Bu)10(OH2)2(DMF)4]·[2MeOH·4DMF]

The reaction of MnCl2·4H2O with t-BuPO3H2 in the presence of triethylamine afforded the tridecanuclear cage, [MnIIMnIII12(μ4-O)6(μ-OH)6(O3P–t-Bu)10(OH2)2(DMF)4]·[2MeOH·4DMF] (1). The structural analysis of 1 reveals that it is a mixed-valent complex containing a [MnIIMnIII12(μ4-O)6] core. The centre of the core is occupied by a MnII ion which is surrounded by 12 MnIII ions. The latter are connected to each other by six μ-OH− and 10 t-BuPO32− ligands. The vacant coordination sites of six MnIII ions situated in the periphery are occupied by four DMF and two water molecules. Magnetic studies on 1 reveal a frequency-dependent response which is characteristic of single-molecule magnets.

Graphical abstractThe synthesis, structure and magnetism of a mixed-valent Mn13 cage are described.Figure optionsDownload full-size imageDownload as PowerPoint slide