Heteroatom‐Doping Increases Cluster Nuclearity: From an [Ag₂₀] to an [Au₃Ag₁₈] Core

A templated galvanic exchange performed on [Ag 20 {Se 2 P(O i Pr) 2 } 12 ] of C 3 symmetry with three equiv Au I yields a mixture of [Au 1+ x Ag 20− x {Se 2 P(O i Pr) 2 } 12 ] + ( x= 0–2) from which [Au@Ag 20 {Se 2 P(O i Pr) 2 } 12 ] + and [Au@Au 2 Ag 18 {Se 2 P(O i Pr) 2 } 12 ] + are successfully characterized to have T and C 1 symmetry, respectively. Crystal structural analyses combined with DFT calculations on the model compounds explicitly demonstrate that the central Ag 0 of Ag 20 being oxidized by Au I migrates to the protecting atomic shell as a new capping Ag I , and both second and third Au dopants prefer occupying non‐adjacent icosahedron vertices. The differences in symmetry, T and C 1 , are manifested in the spatial orientation of their protecting atomic shell composed of eight capping Ag atoms as well as re‐construction upon the replacement of Ag atoms on the vertices of AuAg 12 icosahedral core with second and third Au dopants. As a result, a unique pathway for substitutional‐doped clusters with increased nuclearity is proposed.