Research ArticleChemistry

Valence self-regulation of sulfur in nanoclusters

See allHide authors and affiliations

Science Advances  22 Nov 2019:
Vol. 5, no. 11, eaax7863
DOI: 10.1126/sciadv.aax7863
  • Fig. 1 Structures of Pt1Ag28 nanoclusters.

    Structural anatomies of Pt1Ag28−1 (A to C) and Pt1Ag28-2 (A, D, and E). Color codes: green sphere, Pt; violet sphere, Ag in the icosahedral M13 kernel; blue sphere, Ag in the motif structures; yellow sphere, S; red sphere, O; gray sphere, C. For clarity, the hydrogen atoms are not shown.

  • Fig. 2 “−1” valent sulfur in hydroxylated thiolates.

    Sulfur-oxidation pathway from thiol to sulfonic acid. The “−1” valent sulfur in Pt1Ag28−2 supports the hypothesis that there is an intermediate between the “−2” valent S in thiols (R-SH) and the “0” valent S in sulfenic acids (R-S-OH).

  • Fig. 3 Cocrystallization of nanoclusters.

    (A and B) Cocrystallization of Pt1Ag28−1 and Pt1Ag28−2 in packing mode. The interlayer distance is calculated as 33.978 Å. Views from (C) x direction, (D) y direction, and (E) z direction. Color codes: violet sphere, Ag in Pt1Ag28−1; blue sphere, Ag in Pt1Ag28−2; green sphere, Pt; yellow sphere, S; red sphere, O. For clarity, the carbon and hydrogen atoms are not shown.

  • Fig. 4 ESI-MS results of nanoclusters.

    (A) ESI-MS result of the Pt1Ag28 sample (including Pt1Ag28−1 and Pt1Ag28−2) and the comparison of the experimental and calculated isotopic patterns. (B) ESI-MS result of the deuterated Pt1Ag28 nanoclusters (including Pt1Ag28−1 and Pt1Ag28−2-D) and the comparison of the experimental and calculated isotopic patterns. (C) Comparison of ESI-MS results of Pt1Ag28-H (including Pt1Ag28−1 and Pt1Ag28−2) and Pt1Ag28-D (including Pt1Ag28−1 and Pt1Ag28−2-D). Note that (i) the mass peaks around 6694.01 Da remain (highlighted in gray) because no hydroxyl is bonded on Pt1Ag28−1, and (ii) the 2 Da of the mass gap between the peaks of 6728.01 and 6730.01 Da is precisely the double of the mass peak between H and D (highlighted in orange).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/11/eaax7863/DC1

    Fig. S1. UV-vis, TGA, XPS, IR, 1H NMR, and EPR results of nanoclusters.

    Fig. S2. Packing mode of nanoclusters.

    Fig. S3. ESI-MS details of Pt1Ag28(SR)20 and Pt1Ag28(SR)18(DO-SR)2.

    Fig. S4. ESI-MS of Pt1Ag28(SR)20 and Pt1Ag28(SR)18(H18O-SR)2.

    Fig. S5. ESI-MS of the synthetic procedure.

    Fig. S6. NMR signals of nanoclusters.

    Fig. S7. UV-vis and ESI-MS results of Pt1Ag28(SR)18(PPh3)4.

    Table S1. Atom ratio of Pt and Ag in nanoclusters.

    Table S2. Comparison of bond lengths in nanoclusters.

    Table S3. Crystal data and structure refinement for nanoclusters.

  • Supplementary Materials

    This PDF file includes:

    • Fig. S1. UV-vis, TGA, XPS, IR, 1H NMR, and EPR results of nanoclusters.
    • Fig. S2. Packing mode of nanoclusters.
    • Fig. S3. ESI-MS details of Pt1Ag28(SR)20 and Pt1Ag28(SR)18(DO-SR)2.
    • Fig. S4. ESI-MS of Pt1Ag28(SR)20 and Pt1Ag28(SR)18(H18O-SR)2.
    • Fig. S5. ESI-MS of the synthetic procedure.
    • Fig. S6. NMR signals of nanoclusters.
    • Fig. S7. UV-vis and ESI-MS results of Pt1Ag28(SR)18(PPh3)4.
    • Table S1. Atom ratio of Pt and Ag in nanoclusters.
    • Table S2. Comparison of bond lengths in nanoclusters.
    • Table S3. Crystal data and structure refinement for nanoclusters.

    Download PDF

    Files in this Data Supplement:

Stay Connected to Science Advances

Navigate This Article