A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster
Zhi Wang, Hai‐Feng Su, Yiwen Gong, Qing-Ping Qu, Yanfeng Bi, Chen‐Ho Tung, Di Sun, Lan‐Sun Zheng
Abstract
Abstract 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 Ag 88 nanocluster (SD/Ag88a) built from p -tert-butylthiacalix[4]arene (H 4 TC4A) is reported. Single-crystal X-ray diffraction reveals that C 4 -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 [CrO 4 @Ag 11 (TC4A)(EtS) 4 (OAc)] secondary building units arranged in an annulus encircling a CrO 4 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 Ag 88 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.