Extensive Polymerization of Atomically Precise Alloy Metal Clusters During Solid-State Reactions.

Area of Science:

• Materials Science
• Nanotechnology
• Inorganic Chemistry

Background:

• Research on atomically precise metal clusters has focused on their reactions, primarily in solution phase.
• Solution-phase reactions typically involve dimer formation between reacting clusters.

Purpose of the Study:

• To investigate the solid-state interactions between two specific atomically precise metal clusters: [Au25(PET)18]- and [Ag25(DMBT)18]-.
• To explore the formation of alloy metal clusters and polymers resulting from these solid-state interactions.

Main Methods:

• Solid-state reactions between [Au25(PET)18]- (2-phenylethanethiol) and [Ag25(DMBT)18]- (2,4-dimethylbenzenethiol) were studied using varying cluster ratios.
• Control experiments were conducted to elucidate the reaction mechanisms.

Main Results:

• Solid-state reactions between the specified gold and silver clusters were significantly faster than solution-phase reactions.
• Metal exchange between the clusters in the solid state led to the formation of dimers, trimers, tetramers, and polymers.
• Polymer entities, including hexamers, were observed for the first time, indicating successful polymerization.

Conclusions:

• Solid-state interactions provide a more efficient pathway for reactions between atomically precise metal clusters.
• Metal exchange is the critical factor driving polymerization in these solid-state systems.
• This study presents a novel approach for the synthesis of polymers composed of atomically precise alloy metal clusters.