A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping

摘要: We show, via density functional theory calculations, that dianionic Au162− cluster has a stable, hollow, Td symmetric cage structure, stabilized by 18 delocalized valence electrons. The maintains its robust geometry, with minor Jahn–Teller deformation, over several charge states (q = −1,0,+1), forming spin doublet, triplet and quadruplet according to the Hund’s rules. Endohedral doping of Au16 Al or Si yields geometrically robust, tuneable oxidation reduction agent. Si@Au16 is magic species 20 calculate significant binding energy for anionic Si@Au16/O2− complex show adsorbed O2 activated superoxo-species, result which at variance experimentally well-documented inertness Au16− anion towards oxygen uptake.