Anion-templated nanosized silver clusters protected by mixed thiolate and diphosphine

Area of Science:

• Inorganic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Polynuclear silver clusters are of interest due to their unique structures and potential applications.
• Developing controlled synthesis strategies for these complex clusters remains a challenge.

Purpose of the Study:

• To establish a new strategy for constructing high-symmetry polynuclear silver clusters using anionic templates.
• To explore the influence of template size and shape on cluster nuclearity and geometry.
• To investigate the luminescent properties of the synthesized clusters.

Main Methods:

• Single-crystal X-ray diffraction for structural elucidation.
• High-resolution electrospray mass spectrometry (HR-ESI-MS) for stability analysis.
• Variable-temperature solid-state luminescence spectroscopy.

Main Results:

• Six high-symmetry polynuclear silver clusters were synthesized using S^2-, MoO₄^2-, and Mo₆O₂₂^8- as templates.
• Structures ranged from an octadecanuclear banana-shaped cluster to tetraicosanuclear and a giant 46-silver-atom cluster.
• Cluster 4 exhibited exceptional stability in acetonitrile, and cluster 1 displayed thermochromism.

Conclusions:

• Anionic templates and mixed S-/P-donor ligands provide a versatile strategy for synthesizing diverse polynuclear silver clusters.
• Cluster nuclearity and geometry are tunable by the choice of template.
• The synthesized clusters show promise for developing novel dual emissive materials.