Tailoring two magic number Au13 nanoclusters with N-containing diphosphine ligands: a classical icosahedral core vs. an unprecedented UFO- shaped core

Abstract

Two magic number Au₁₃ nanoclusters, [Au₁₃(PNP)₅Cl₂]Cl₃ and [Au₁₃(Hdppa)₆]Cl₅, with the same nuclearity number but completely distinct configurations, were elaborately constructed using N-containing diphosphine ligands (PNP or Hdppa). Significantly, the metal core of [Au₁₃(PNP)₅Cl₂]³⁺ is a classical Au₁₃ icosahedron, while the [Au₁₃(Hdppa)₆]⁵⁺ core presents a “UFO”-shaped polyhedron, which is illuminated here for the first time. The “UFO”-shaped Au₁₃ core is also unprecedented among 13-atom coinage-metal clusters. The luminescence of [Au₁₃(PNP)₅Cl₂]Cl₃ is at 732 nm in solution and 750 nm in the solid state, close to the near-infrared region. Moreover, the luminescence lifetimes are longer than those of reported icosahedral Au₁₃ nanoclusters. This work demonstrates that N-functionalization of phosphine ligands is one of the effective methods for tailoring atomically precise gold clusters.