Total Synthesis of Thiolate‐Protected Noble Metal Nanoclusters

Thiolate-protected noble metal nanoclusters (NCs) are a family of ultra-small particles with a core size of 3nm or lower, representing the missing link between discrete metal atoms and metal nanocrystals. This chapter employs thiolate-protected noble metal NCs as paradigm particles and exemplifies the state-of-the-art development of total synthesis chemistry of metal nanoparticles at the molecular and atomic levels. It starts discussion with a concise summary on the engineering chemistry of the cluster size, followed by the principles governing the composition customization of metal NCs. Besides the growth and functionalization chemistry, the chapter also exemplifies the decomposition chemistry of metal NCs in the presence of etchant, which is crucial in stabilization and application of metal NCs. Due to its molecule-like nature, metal NCs exhibit highly size-dependent properties.