Rational construction of a library of M 29 nanoclusters from monometallic to tetrametallic

Exploring intermetallic synergy has allowed a series of alloy nanoparticles with prominent chemical–physical properties to be produced. However, precise alloying based on a maintained template has long been a challenging pursuit, and little has been achieved for manipulation at the atomic level. Here, a nanosystem based on M 29 (S-Adm) 18 (PPh 3 ) 4 (where S-Adm is the adamantane mercaptan and M is Ag/Cu/Au/Pt/Pd) has been established, which leads to the atomically precise operation on each site in this M 29 template. Specifically, a library of 21 species of nanoclusters ranging from monometallic to tetrametallic constitutions has been successfully prepared step by step with in situ synthesis, target metal-exchange, and forced metal-exchange methods. More importantly, owing to the monodispersity of each nanocluster in this M 29 library, the synergetic effects on the optical properties and stability have been mapped out. This nanocluster methodology not only provides fundamental principles to produce alloy nanoclusters with multimetallic compositions and monodispersed dopants but also provides an intriguing nanomodel that enables us to grasp the intermetallic synergy at the atomic level.