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

Exploring the reactions between atomically precise metal clusters and the consequences of such reactions has been an exciting field of research during the past decade. Initial studies in the area were on reactions between clusters in the solution phase, which proceed through the formation of dimers of reacting clusters. In the present work, we examine the interaction between two atomically precise clusters, [Au 25 (PET) 18 ] - and [Ag 25 (DMBT) 18 ] - , in the solid state, where PET and DMBT are 2-phenylethanethiol and 2,4-dimethylbenzenethiol, respectively. The experiments were performed using different ratios of these two clusters, and it was inferred that the kinetics of the reactions were faster compared with reactions in the solution. The metal exchange between these two clusters, due to their interactions in the solid state, leads to the formation of dimers, trimers, tetramers, and polymers of atomically precise alloy metal clusters. We observed polymer entities up to hexamers, which were observed for the first time. Control experiments revealed that metal exchange is a key factor leading to polymerization. Our work points to a new approach for synthesizing polymers of atomically precise alloy metal clusters.