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. 2020 Jan 16;11(1):308.
doi: 10.1038/s41467-019-13682-5.

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

Zhi Wang  1 , Hai-Feng Su  2 , Yi-Wen Gong  1 , Qing-Ping Qu  1 , Yan-Feng Bi  3 , Chen-Ho Tung  1 , Di Sun  4 , Lan-Sun Zheng  2
Affiliations

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

Zhi Wang et al. Nat Commun. .

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.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Synthetic route for super calix of SD/Ag88a.
DCM = dichloromethane, DMF = N,N-dimethylformamide. Color legends for objects: red: H4TC4A ligand; green: super calix; pink: silver atom; blue: CrO42−; yellow: the base of super calix.
Fig. 2
Fig. 2. Single-crystal X-ray structure of SD/Ag88a.
a and b Total structures of Ag88 super calix viewed along two orthogonal directions. The inset in Fig. 2a is the photograph of crystals of SD/Ag88a taken by using a digital camera under the microscope. c and d The skeletal structure of SD/Ag88a by removing all organic ligands and anion templates viewed along two orthogonal directions. Color labels: purple, Ag; yellow, S; gray, C; red, O; green polyhedra, CrO42−.
Fig. 3
Fig. 3. Ag11 SBU in SD/Ag88a.
a The ball-and-stick mode of the structure of [CrO4@Ag11(TC4A)(EtS)4(OAc)] SBU. b, c Two different coordination modes of TC4A4− ligands. Color labels: purple, Ag; yellow, S; gray, C; red, O; cyan, Cr. d The Ag88 annulus built from eight Ag11 SBUs around the central CrO42− anion. Eight Ag11 SBUs are individually colored.
Fig. 4
Fig. 4. The packing of SD/Ag88a and SD/Ag88b.
Top and side views of the 1D array of SD/Ag88a (a, c) and SD/Ag88b (b, d). Different Ag88 clusters are individually colored. The central CrO42− was removed for clarity.
Fig. 5
Fig. 5. Positive-ion ESI-MS and proposed solution assembly mechanism of SD/Ag88a.
a Positive-ion ESI-MS of SD/Ag88a dissolved in CH2Cl2. Inset: the expanded experimental and simulated isotope-distribution patterns of 1a–1g. b The proposed solution assembly mechanism for SD/Ag88a.
Fig. 6
Fig. 6. The UV–Vis spectra and photocurrent responses of SD/Ag88a and SD/Ag88b.
a The normalized UV–Vis spectra of SD/Ag88a, SD/Ag88b, and (EtSAg)n precursor in the solid state. Insets are the digital photographs of SD/Ag88a, SD/Ag88b, and (EtSAg)n taken under the ambient environment. b Compared photocurrent responses of blank, (EtSAg)n, SD/Ag88a, and SD/Ag88b ITO electrodes in a 0.2 M Na2SO4 aqueous solution under repetitive irradiation.
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