From pseudo to true C(3) symmetry: magnetic anisotropy enhanced by site-specific ligand substitution in two Mn(15)-carboxylate clusters

Inorg Chem. 2007 Aug 6;46(16):6437-43. doi: 10.1021/ic7004584. Epub 2007 Jul 13.

Abstract

Two new mixed-valence manganese-carboxylate clusters, [MnIII9MnIV6(O2CPh)12(micro3-O)13(micro-O)4(micro-OMe)5(MeOH)4(H2O)5]2.1.5PhCO2H.MeOH.6H2O (1, PhCO2H = benzoic acid) and [MnIII9MnIV6(O2CCh)12(micro3-O)13(micro-O)4(micro-OMe)5(MeOH)3(H2O)6].0.5MeOH.2.5H2O (2, ChCO2H= cyclohexanecarboxylic acid) contain new disklike Mn15 cores. Both 1 and 2 can be synthesized by the conventional manganese redox reaction (MnO4- oxidizing Mn2+) in methanol solution. 2 can be also synthesized via the site-specific ligand substitution reaction from 1. 1 crystallizes in the triclinic space group P, whereas 2 crystallizes in the trigonal space group P. Magnetic study shows that both 1 and 2 have the same ground spin states ST = 2. Compared to the silence of the out-of-phase ac susceptibility of 1, 2 shows clearly slow magnetic relaxation behavior above 1.8 K due to the dramatically enhanced axial magnetic anisotropy (D = -0.89 and -1.58 cm-1 for 1 and 2, respectively, which was obtained by fitting the plots of M vs H/T with the program ANISOFIT 2.0).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anisotropy*
  • Carbon / chemistry*
  • Carboxylic Acids / chemistry
  • Crystallization
  • Crystallography, X-Ray
  • Ligands
  • Magnetics*
  • Manganese / chemistry*
  • Methanol / chemistry
  • Models, Molecular
  • Models, Statistical
  • Molecular Conformation
  • Oxidation-Reduction

Substances

  • Carboxylic Acids
  • Ligands
  • Manganese
  • Carbon
  • Methanol