Cubic aromaticity in ligand-stabilized doped Au superatoms

The magnetic response of valence electrons in doped gold-based M@Au8L8q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L PPh3; q 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) framework auxiliary density functional theory. systems include 24 different combinations dopant, total cluster charge, structure (cubic-like or oblate). (both diatropic paratropic) are shown to be sensitive atomic clusters, number superatomic electrons, chemical nature dopant metal. Among cubic-like structures, strongest aromaticity observed Pd- Pt-doped M@Au8L80 clusters. Interestingly, Pt-doping increases as compared a similar all-gold eight-electron system Au9L8+1. With recent implementation GIMIC deMon2k code, we investigated cubic butterfly-like M@Au8 core with single M atom from periods 5 6 groups IX–XII. Surprisingly, doping Pd Pt pure Au case not only near central but encompassing whole metallic core, following aromatic trend > Au. These (Pd, Pt)@Au8 nanoclusters show closed shell 1S21P6 superatom electronic corresponding rule 6n + 2.