Ligand-Protected Gold Alloy Clusters: Doping the Superatom

A density functional study of the experimentally observed ligand-protected gold alloy clusters PdAu 12 (PR 3 ) 8 Cl 4 and PtAu 6 Ag 6 (AgI 3 ) 2 (PR 3 ) 6 reveal the same stabilization mechanism as in ligand protected pure Au N: the delocalized s-electron subsystem of a high symmetry metal core exhibits a shell closing. On the basis of this observation it is predicted that the substitution of a single Au atom in the well-known Au 25 (SR) 18 compound with Pd, Ag, and Cd will produce stable clusters resulting in a method to tune redox properties in such a nanoscale building block.