Giant Core–Shell Nanospherical Clusters Composed of 32 Co or 32 Ni Atoms Held by 6 p-tert-Butylthiacalix[4]arene Units

Using combinations of p-tert-butylthiacalix­[4]­arene (TCA) and [M­(DMSO)6(BF4)2] salts (M = CoII or NiII), two almost isostructural core–shell-type thermally stable giant nanoclusters, composed of 32 metal centers, 6 deprotonated calix units binding the metal centers by both their O and S atoms, 24 μ-oxo or μ-hydroxo bridging groups, and 6 MeOH molecules, have been prepared under mild and reproducible conditions. For both giant clusters, the oxidation state II [MII32O16(OH)8(CH3OH)6TCA6 (M = Co or Ni)] for the metal center was demonstrated by X-ray photoelectron and electronic absorption spectroscopies.