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NHC-Stabilized Au10 Nanoclusters and Their Conversion to Au25 Nanoclusters.

Paul A Lummis1, Kimberly M Osten2, Tetyana I Levchenko1

  • 1Department of Chemistry, Queen's University, Chernoff Hall, Kingston, Ontario K7L 3N6, Canada.

JACS Au
|May 13, 2022
PubMed
Summary

We synthesized toroidal gold (Au10) clusters using N-heterocyclic carbene ligands. Halide ligands influenced cluster formation and stability, with bromide and iodide derivatives forming larger Au25 clusters.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Gold clusters are promising nanomaterials with unique optical and electronic properties.
  • Stabilization of gold clusters with ligands is crucial for controlling their structure and reactivity.
  • N-heterocyclic carbene (NHC) ligands offer robust stabilization for metal clusters.

Purpose of the Study:

  • To synthesize and characterize toroidal gold (Au10) clusters stabilized by NHC and halide ligands.
  • To investigate the influence of different halide ligands (Cl, Br, I) on cluster formation, stability, and transformation.
  • To explore the photophysical properties of the resulting gold clusters.

Main Methods:

  • Synthesis of Au10 clusters via reduction of NHC-Au-X complexes (X = Cl, Br, I).
  • Characterization using NMR spectroscopy (including 13C-labeling) and density functional theory (DFT) computations.
  • Investigation of cluster stability and conversion under varying conditions.

Main Results:

  • Toroidal Au10 clusters were successfully synthesized and stabilized by NHC and halide ligands.
  • Chloride ligands yielded stable Au10 clusters, while bromide and iodide facilitated conversion to Au25 clusters.
  • The isolated Au25 cluster exhibited a notable photoluminescence quantum yield (~15%) due to structural rigidity.

Conclusions:

  • Halide ligands play a critical role in directing the formation and stability of NHC-stabilized gold clusters.
  • The bromide derivative of Au25 shows potential for applications in luminescence-based technologies.
  • DFT calculations provide insights into the electronic structure and optical properties of the synthesized gold clusters.