Transformation Chemistry of Gold Nanoclusters: From One Stable Size to Another

Controlling nanoparticles with atomic precision has long been a major dream of nanochemists. This dream has first been realized in the case of gold nanoparticles. We previously discussed a size-focusing methodology for the syntheses of atomically precise gold nanoclusters protected by thiolate ligands (referred to as Aun(SR)m, where n and m represent the exact numbers of gold atoms and surface ligands). This methodology led to molecularly pure nanoclusters such as Au25(SR)18, Au38(SR)24, Au144(SR)60, and many others in recent work. In this Perspective article, we shall further discuss a new methodology for controlling the size and structure of nanoclusters through ligand-exchange-induced transformation of Aun(SR)m nanoclusters. Notable examples include the transformations of Au25(SR)18 to Au28(SR')20, Au38(SR)24 to Au36(SR')24, and Au144(SR)60 to Au133(SR')52. Total structures of the new nanoclusters have also been attained. The transformation processes are remarkable and resemble the organic transformation chemistry. We have also achieved mechanistic understanding on the transformation process, and a disproportionation mechanism has been for the first time identified. This new methodology (i.e., ligand-exchange-induced size/structure transformation, LEIST for short) has not only demonstrated the important role of thiolate ligand in the transformation chemistry of clusters but also paved the way for creating an expanded "library" of Aun(SR)m nanoclusters for exploration of their magic sizes, structures, properties, and applications.