Research ArticleNANOMATERIALS

Thiacalix[4]arene: New protection for metal nanoclusters

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Science Advances  12 Aug 2016:
Vol. 2, no. 8, e1600323
DOI: 10.1126/sciadv.1600323
  • Scheme 1 Structure of thiacalix[4]arene H4L.
  • Fig. 1 Representative crystal structure of [Ag35(H2L)2(L)(C≡CBut)16]3+ cluster.

    (A) Overall structure of cationic cluster 1. (B) Space-filling view of the metal core structure. (C) The arrangement of thiacalixarene ligands and the metal core. Pink/green, silver; red, oxygen; yellow, sulfur; gray/blue, carbon; bright green, chloride. Dash line represents hydrogen bonding. The hydrogen atoms were omitted for clarity.

  • Fig. 2 The arrangements of metal core and ligands.

    (A to D) Top view: Position of 10 peripheral Ag atoms (green) held by thiacalixarene ligands onto the Ag13 core (pink) (A and C). Bottom view: Position of 12 peripheral Ag atoms (green, triangular prisms) capped by alkynyl ligands (B and D). (E and F) Top and side views of the position of surface ligands with respect to the Ag35 core. Purple, sphere, Ag35 core; blue, thiacalixarene ligand; gray, alkynyl ligand.

  • Fig. 3 The coordination motifs A and B of the thiacalix[4]arene with silver atoms.

    The silver atoms in pink belong to the Ag13 core.

  • Fig. 4 ESI-MS spectra.

    (A) Experimental (blue) and simulated (red) spectra of [Ag35(H2L)2(L)(C≡CBut)16]3+ (1). (B) Formation of Ag36 cluster by addition of 2 equiv of NEt3 and 1 equiv of AgSbF6 to Ag35. (C) The deprotonated product of 1 by addition of 2 equiv of NEt3. (D) Formation of Ag34 cluster by addition of 2 equiv of HBF4 to Ag35.

  • Fig. 5 TEM image of 1.
  • Scheme 2 Transformation among Ag34, Ag35 and Ag36 cluster species.

    The alkynyl ligands have been omitted for clarity.

  • Fig. 6 The optical absorption spectra of Ag35 and analogous Ag34 and Ag36 species in CH2Cl2.

    Abs., absorbance.

  • Fig. 7 The experimental absorption in comparison with the calculated spectrum of Ag35.

    a.u., arbitrary unit.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/2/8/e1600323/DC1

    Supplementary Materials and Methods

    table S1. Crystal data and structure refinement for 1.

    fig. S1. The experimental and simulated PXRD spectra of 1.

    fig. S2. Infrared spectrum of 1.

    fig. S3. EDX analysis of 1.

    fig. S4. 1H nuclear magnetic resonance spectrum of 1 (CD3COCD3).

    fig. S5. The coordination modes of alkynyl ligands in 1.

    fig. S6. The main frontier orbitals of Ag34, Ag35, and Ag36 clusters.

    fig. S7. The experimental absorption spectra in comparison with calculated spectra of Ag34 (left) and Ag36 (right).

  • Supplementary Materials

    This PDF file includes:

    • Supplementary Materials and Methods
    • table S1. Crystal data and structure refinement for 1.
    • fig. S1. The experimental and simulated PXRD spectra of 1.
    • fig. S2. Infrared spectrum of 1.
    • fig. S3. EDX analysis of 1.
    • fig. S4. 1H nuclear magnetic resonance spectrum of 1 (CD3COCD3).
    • fig. S5. The coordination modes of alkynyl ligands in 1.
    • fig. S6. The main frontier orbitals of Ag34, Ag35, and Ag36 clusters.
    • fig. S7. The experimental absorption spectra in comparison with calculated spectra of Ag34 (left) and Ag36 (right).

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