Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu₄ and Au@Ag₄ Clusters Supported by...

We report herein a family of polynuclear complexes, [Au@Ag₄(Py₃P)₄]X₅ and [Au@Cu₄(Py₃P)₄]X₅ [X = NO₃, ClO₄, OTf, BF₄, SbF₆], containing unprecedented Au-centered Ag₄ and Cu₄ tetrahedral cores supported by tris(2-pyridyl)phosphine (Py₃P) ligands. The [Au@Ag₄]⁵⁺ clusters are synthesized via controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag₄]⁵⁺ precursors by the reaction with Au(tht)Cl, while the [Au@Cu₄]⁵⁺ cluster is assembled through the treatment of a pre-organized [Au(Py₃P)₄]⁺ metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M₄ clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions. At ambient temperature, the designed compounds emit a modest turquoise-to-yellow luminescence with microsecond lifetimes. Based on the temperature-dependent photophysical experiments and DFT/TD-DFT computations, the emission observed has been assigned to an MLCT or LLCT type depending on composition of the cluster core.