[Mn14] “Structural Analogues” of Well-Known [Mn12] Single-Molecule Magnets

Abstract

A new family of tetradecanuclear Mn clusters [MnIII10MnIV4(µ3-O)12(EtCO2)12(pd)4(EtOH)4(py)4](ClO4)2 (1), [MnIII10MnIV4(µ3-O)12(EtCO2)12(mpd)4(EtOH)2(H2O)2(py)4](ClO4)2 (2), and [MnIII10MnIV4(µ3-O)12(MeCO2)10(pic)4(pd)4(pdH2)4] [3] (picH = picolinic acid) were prepared from the use of the aliphatic diols 1,3-propanediol (pdH2) and 2-methyl-1,3-propanediol (mpdH2). The [MnIII10MnIV4] aggregates consist of a [MnIII10] outer ring surrounding a [MnIV4] defective dicubane. Interestingly, the core of 1?3 is similar to those of a [Mn12(µ3-O)12(RCO2)16(H2O)4] ?normal [Mn12]? and a modified [Mn12] aggregate consisting of a [MnIII8] ring, surrounding a [MnIV4] defective dicubane called ?flat [Mn12]?. Dc and ac magnetic susceptibility studies revealed the presence of dominant antiferromagnetic exchange interactions in complexes 1?3 leading to small spin ground-state values.