Nanocluster reaction-driven in situ transformation of colloidal nanoparticles to mesostructures

Atomically precise noble metal nanoclusters (NCs) are molecular materials known for their precise composition, electronic structure, and unique optical properties, exhibiting chemical reactivity. Herein, we demonstrated a simple one-pot method for fabricating self-assembled Ag-Au bimetallic mesostructures using a reaction between 2-phenylethanethiol (PET)-protected atomically precise gold NCs and colloidal silver nanoparticles (Ag NPs) in a tunable reaction microenvironment. The reaction carried out in toluene at 45 °C with constant stirring at 250 revolutions per minute (RPM) yielded a thermally stable, micron-sized cuboidal mesocrystals of self-assembled AgAu@PET nanocrystals. However, the reaction in dichloromethane at room temperature with constant stirring at 250 RPM resulted in a self-assembled mesostructure of randomly close-packed AgAu@PET NPs. Using a host of experimental techniques, including optical and electron microscopy, optical absorption spectroscopy, and light scattering, we studied the nucleation and growth processes. Our findings highlight a strategy to utilize precision and plasmonic NP chemistry in tailored microenvironments, leading to customizable bimetallic hybrid three-dimensional nanomaterials with potential applications.