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

Zhi Wang, Hai-Feng Su, Yi-Wen Gong, Qing-Ping Qu, Yan-Feng Bi, Chen-Ho Tung, Di Sun () and Lan-Sun Zheng
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Zhi Wang: State Key Laboratory of Crystal Materials, Shandong University
Hai-Feng Su: Xiamen University
Yi-Wen Gong: State Key Laboratory of Crystal Materials, Shandong University
Qing-Ping Qu: State Key Laboratory of Crystal Materials, Shandong University
Yan-Feng Bi: Liaoning Shihua University
Chen-Ho Tung: State Key Laboratory of Crystal Materials, Shandong University
Di Sun: State Key Laboratory of Crystal Materials, Shandong University
Lan-Sun Zheng: Xiamen University

Nature Communications, 2020, vol. 11, issue 1, 1-8

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 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 TC4A4− 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 CrO42− 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 TC4A4−. This work not only exemplify the specific macrocyclic effects of TC4A4− in the construction of silver nanocluster but also realize the shape heredity of TC4A4− to overall silver super calix.

Date: 2020
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DOI: 10.1038/s41467-019-13682-5

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