Filling the gaps in icosahedral superatomic metal clusters.

Chemically modified superatoms have emerged as promising candidates in the new periodic table, in which Au(13) and its doped M (n) Au(13-) (n) have been widely studied. However, their important counterpart, Ag(13) artificial element, has not yet been synthesized. In this work, we report the synthesis of Ag(13) nanoclusters using strong chelating ability and rigid ligands, that fills the gaps in the icosahedral superatomic metal clusters. After further doping Ag(13) template with different degrees of Au atoms, we gained insight into the evolution of their optical properties. Theoretical calculations show that the kernel metal doping can modulate the transition of the excited-state electronic structure, and the electron transfer process changes from local excitation (LE) to charge transfer (CT) to LE. This study not only enriches the families of artificial superatoms, but also contributes to the understanding of the electronic states of superatomic clusters.