A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

Thiacalix[4]arenes as a family of promising ligands have been widely used to construct polynuclear metal clusters, but scarcely employed in silver nanoclusters. Herein, an anion-templated Ag₈₈ nanocluster (SD/Ag88a) built from p-tert-butylthiacalix[4]arene (H₄TC4A) is reported. Single-crystal X-ray diffraction reveals that C₄-symmetric SD/Ag88a resembles a metal-organic super calix comprised of eight TC4A^4- as walls and 88 silver atoms as base, which can be deconstructed to eight [CrO₄@Ag₁₁(TC4A)(EtS)₄(OAc)] secondary building units arranged in an annulus encircling a CrO₄^2- in the center. Local and global anion template effects from chromates are individually manifested in SD/Ag88a. The solution stability and hierarchical assembly mechanism of SD/Ag88a are studied by using electrospray mass spectrometry. The Ag₈₈ nanocluster represents the highest nuclearity metal cluster capped by TC4A^4-. This work not only exemplify the specific macrocyclic effects of TC4A^4- in the construction of silver nanocluster but also realize the shape heredity of TC4A^4- to overall silver super calix.