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.采用对叔丁基硫杂杯[4]芳烃（p-tert-butylthiacalix[4]arene，TCA）与[M(DMSO)6(BF4)2]盐（M = CoII或NiII）的组合体系，在温和且可重复的反应条件下，成功制备了两例近乎同构的核壳型热稳定巨型纳米团簇。该类团簇由32个金属中心、6个去质子化杯芳烃单元（通过氧原子与硫原子与金属中心配位）、24个μ-氧桥或μ-羟桥联基团，以及6个甲醇分子构成。通过X射线光电子能谱与电子吸收光谱，证实了这两例巨型团簇的金属中心均为二价氧化态，对应分子式为[MII32O16(OH)8(CH3OH)6TCA6]（M = Co或Ni）。