Mechanism of Metal Exchange in Non-metallic Nanoclusters
Metal nanoclusters have been served as an emerging class of modular nanomaterials owing to their atomically precise structures, fascinating properties, and potential applications. Among the nanocluster science, the subject of nanocluster alloying represents one of the most dynamic areas and has emerged recently as a new “growth point”. The metal-exchange strategy, i.e., doping a template nanocluster with the thiolated metallic complexes as the heteroatom source, has been extensively exploited in the preparation of new alloy nanoclusters. However, the mechanism of this metal-exchange process has not been elucidated.In this work,We substituted gold atoms in fcc structured Au28 and Au36 nanoclusters with Ag(I)SR complex, and obtained AgxAu28-x and AgxAu36-x nanoclusters, respectively. The positive electrostatic potential (ESP) and dual descriptor (△f) values were calculated for the metal cores for both nanoclusters, which indicated that the metal exchange is an electrophilic reaction.