A Homoleptic Alkynyl-Ligated [Au₁₃ Ag₁₆ L₂₄ ]^3- Cluster as a Catalytically Active Eight-Electron Superatom

Area of Science:

• Nanotechnology and Materials Science
• Inorganic Chemistry
• Catalysis

Background:

• Gold-silver clusters are of interest due to their unique electronic and optical properties.
• Ligand design is crucial for stabilizing and functionalizing metal clusters.
• Superatom chemistry offers a framework for understanding cluster properties.

Purpose of the Study:

• To synthesize and characterize a new alkynylated gold-silver cluster.
• To investigate the electronic, optical, and catalytic properties of the synthesized cluster.
• To explore the potential of the cluster as a catalyst for A3-coupling reactions.

Main Methods:

• NaBH4 mediated reduction for cluster synthesis.
• Advanced characterization techniques (e.g., X-ray crystallography, spectroscopy).
• Density Functional Theory (DFT) calculations for electronic structure analysis.
• Catalytic testing for A3-coupling reactions.

Main Results:

• A novel alkynylated cluster [Au13Ag16(C10H6NO)24]3- with a unique metal framework was successfully synthesized.
• The cluster exhibits distinct electronic and optical properties, consistent with superatom theory (8-electron superatom).
• The supported Au13Ag16L24/CeO2 catalyst demonstrated high activity and selectivity in the A3-coupling reaction.

Conclusions:

• The study presents a new synthetic route to complex gold-silver clusters with atypical ligand protection.
• The electronic and optical properties are well-described by superatom models.
• The developed catalyst shows significant promise for efficient synthesis of valuable chemical intermediates.