A family of mixed-valent MnIVMn6IIIMn6II tridecanuclear clusters, and their magnetostructural correlation

Three tridecanuclear Mn complexes [Mn13O8(OH)6(ndc)6] · 8DMF · H2O (1), [Mn13O8(EtO)5.5(OH)0.5(ndc)6] · 6MeCN · 2H2O (2), and [Mn13O8(EtO)6(O2CPh)12] · 7H2O (3) (ndc2− = 1,8-naphthalenedicarboxylate) are reported. Complexes 1–3 possess a central core comprised of three layers: The middle layer is a central MnIV atom surrounded by a planar ring of six MnII atoms, and above and below this are two MnIII3 triangular units. Complexes 1 and 2 represent the first use of ndc2− in manganese chemistry. All three complexes are mixed-valent MnIVMn6IIIMn6II. Complex 1 was found to have a ground state spin of S = 9/2, whereas 2 and 3 have S = 11/2 despite the nearly isostructural core of the three compounds. A magnetostructural correlation has shown that small structural perturbations can considerably change the magnetic properties of these clusters.

Three mixed-valent (MnIVMn6IIIMn6II) complexes [Mn13O8(OH)6(ndc)6] (1), [Mn13O8(EtO)5.5(OH)0.5(ndc)6] (2), and [Mn13O8(O2CPh)12(EtO)6] (3) have been synthesized and studied. Complexes 1, 2, and 3 have S = 9/2, 11/2, and 11/2 ground states, respectively. A qualitative magnetostructural correlation allows insights as to the structural origin of the differences in magnetic properties.Figure optionsDownload as PowerPoint slide