Doping-Mediated Energy-Level Engineering of M@Au₁₂ Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and...

We synthesized a series of MAu₁₂ (dppe)₅ Cl₂ (MAu₁₂ ; M=Au, Pd, Pt, Rh, or Ir; dppe=1,2-bis(diphenylphosphino)ethane), which have icosahedral M@Au₁₂ superatomic cores, and systematically investigated their electronic structures, photoluminescence (PL) and photocatalytic properties. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) was expanded when doping an M element positioned at the lower left of the periodic table. The PL quantum yield was enhanced with an increase in the HOMO-LUMO gap and reached 0.46-0.67 for MAu₁₂ (M=Pt, Rh, or Ir) under deaerated conditions. The bright PLs from MAu₁₂ (M=Pt, Rh, or Ir) were assigned to phosphorescence based on quenching by O₂ . MAu₁₂ (M=Pt, Rh, or Ir) acted as a more efficient and stable photocatalyst than Au₁₃ for intramolecular [2+2] cycloaddition of bisenone via the oxidative quenching cycle. This study provides rational guides for designing photoluminescent and photocatalytic gold superatoms by the doping of heterometal elements.