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Structural patterns at all scales in a nonmetallic chiral Au133(SR)52 nanoparticle

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Science Advances  20 Mar 2015:
Vol. 1, no. 2, e1500045
DOI: 10.1126/sciadv.1500045
  • Fig. 1 Total structure of chiral Au133(SR)52 nanoparticle characterized by x-ray crystallography.

    (A) An enantiomer of the chiral Au133(SR)52 nanoparticle. Magenta: gold; yellow: sulfur; gray: carbon; white: hydrogen. (B) Ensemble packing of Au133(SR)52 nanoparticles in PEmbedded Image space group. The left- and right-handed enantiomers are indicated in magenta and green.

  • Fig. 2 The four-shell structure of Au133(SR)52.

    (A to D) The first icosahedral shell with 12 Au atoms (pink) (A); second icosahedral shell with 42 Au atoms (gray) (B); third shell with 52 Au atoms (blue and cyan) (C); fourth shell with 26 Au atoms (orange) and 52 sulfur atoms (yellow) (D). (E) Layered a-b-c-b packing of Au atoms in a tetrahedral unit of an icosahedron; total of 16 such units. (F) a-b-c-a packing of atoms; total of four such units. (G) Monomeric –SR–Au–SR– motifs clamping on the third shell gold atoms. Carbon groups are omitted for clarity.

  • Fig. 3 Self-assembled –S–Au–S– helical stripes on the spherical Au107 kernel.

    (A and B) Side views. (C and D) Top views. The two chiral isomers are shown in (D). Each stripe is composed of six monomeric staples stacked into a ladder-like helical structure. Yellow: sulfur; orange/red/blue/green: gold in the helices; purple: gold in the independent monomeric staples.

  • Fig. 4 Chiral self-assembly of the carbon tails of the SPh-p-But ligands.

    (A) The rotative arrangement of phenyl rings results in the formation of fourfold swirls. (B) Carbon-tail swirls on the square unit; top: left-handed isomer; bottom: right-handed isomer. Yellow: sulfur.

  • Fig. 5 Optical properties of Au133(SR)52 nanoparticles.

    (A) The dashed lines represent peak positions extracted from fitting to a series of inhomogeneously broadened transitions and a nonresonant scatter background. (B) Image plot of transient absorption data with optical pumping at 420 nm, along with representative kinetics (absolute value) at wavelengths corresponding to the dashed lines in the image plot (right panel) and transient spectra (bottom panel) at 1 ps. (C and D) Normalized decay kinetics as a function of laser fluence with 500-nm pump pulses (C) and extracted values of the rate constant for the faster decay component of a two-exponential fit showing the fluence independence of the carrier dynamics (D).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/1/2/e1500045/DC1

    Materials and Methods

    Fig. S1. Electrospray ionization mass spectrum of Au133(SR)52 nanoparticles.

    Table S1. Au-Au bond lengths in the Au107 kernel.

    Table S2. Sample and crystal data for Au133.

    Table S3. Data collection and structure refinement for Au133.

    Table S4. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å2) for Au133.

  • Supplementary Materials

    This PDF file includes:

    • Materials and Methods
    • Fig. S1. Electrospray ionization mass spectrum of Au133(SR)52 nanoparticles.
    • Table S1. Au-Au bond lengths in the Au107 kernel.
    • Table S2. Sample and crystal data for Au133.
    • Table S3. Data collection and structure refinement for Au133.
    • Table S4. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å2) for Au133. U(eq) is defined as one-third of the trace of the orthogonalized Uij tensor.

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