Single-atom "surgery" on chiral all-dialkynyl-protected superatomic silver nanoclusters

Area of Science:

• Nanomaterials Science
• Supramolecular Chemistry
• Chiroptical Spectroscopy

Background:

• Single-atom manipulation in metallic nanocluster kernels offers insights into structure-property relationships.
• Chiral ligands are crucial for stabilizing and characterizing superatomic nanoclusters.

Purpose of the Study:

• To investigate the impact of a single-atom difference on the structure and chiroptical properties of silver nanoclusters.
• To explore the role of chiral bialkynyl ligands in stabilizing superatomic silver nanoclusters.

Main Methods:

• Synthesis and isolation of chiral silver nanoclusters (Ag39 and Ag40) using bialkynyl ligands.
• X-ray diffraction analysis to determine cluster structures.
• Spectroscopic analysis to study optical properties and near-infrared emission.

Main Results:

• Identified analogous silver skeletons in Ag39 and Ag40 nanoclusters, differing by a single silver atom.
• Observed reduced symmetry and enhanced asymmetry g-factor in Ag40 due to the extra atom.
• Reported a red-shift in near-infrared emission from 1088 nm to 1150 nm in Ag40, linked to altered electronic transitions.

Conclusions:

• A single-atom difference significantly impacts nanocluster symmetry, chiroptical properties, and excited-state transitions.
• Bialkynyl ligands are effective in stabilizing superatomic metal nanoclusters and enabling single-atom level studies.
• This research provides fundamental understanding of structure-property correlations in nanomaterials.