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

Wang, Zhi; Su, Hai-Feng; Gong, Yi-Wen; Qu, Qing-Ping; Bi, Yan-Feng; Tung, Chen-Ho; Sun, Di; Zheng, Lan-Sun · Nat Commun · 2020

basic_science · Level V

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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<sub>88</sub> nanocluster (SD/Ag88a) built from p-tert-butylthiacalix[4]arene (H<sub>4</sub>TC4A) is reported. Single-crystal X-ray diffraction reveals that C<sub>4</sub>-symmetric SD/Ag88a resembles a metal-organic super calix comprised of eight TC4A<sup>4-</sup> as walls and 88 silver atoms as base, which can be deconstructed to eight [CrO<sub>4</sub>@Ag<sub>11</sub>(TC4A)(EtS)<sub>4</sub>(OAc)] secondary building units arranged in an annulus encircling a CrO<sub>4</sub><sup>2-</sup> 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<sub>88</sub> nanocluster represents the highest nuclearity metal cluster capped by TC4A<sup>4-</sup>. This work not only exemplify the specific macrocyclic effects of TC4A<sup>4-</sup> in the construction of silver nanocluster but also realize the shape heredity of TC4A<sup>4-</sup> to overall silver super calix.