Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates

Abstract The established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72 , using two and three different anion templates, respectively. Ag57 features a gyroscope‐like monovalent cation with an Ag 3 triangle core sandwiched by one [SiW 9 O 34 ] 10− and a triad of Cl − anion templates. By intentionally introducing the third anion template, SO 4 2− , the structure is expanded to the unprecedented Ag72 (with 15 silver atoms epitaxially grown on top of Ag57 ) resembling a tumbler, inside of which two Ag 3 layers are laminated by one [SiW 9 O 34 ] 10− , seven Cl − and one SO 4 2− anion templates in parallel with respect to longitudinal orientation. It is noteworthy that Ag72 exhibits remarkable structural complexity and represents a pioneering achievement as the first silver cluster incorporating three distinct types of anion templates. In addition, Ag72 demonstrates a significant advantage over Ag57 , particular in terms of applications such as luminescent thermometers and remote laser ignition. This work not only broadens the horizon for precise control of the silver cluster structures through the integration of multiple types of hetero‐anions but also lays a solid foundation for potential optical applications in the future.