Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu and Au@Ag Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag(PyP)]X and [Au@Cu(PyP)]X [X = NO, ClO, OTf, BF, SbF], containing unprecedented Au-centered Ag and Cu tetrahedral cores supported by tris(2-pyridyl)phosphine (PyP) ligands. The [Au@Ag] clusters are synthesized controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag] precursors by the reaction with Au()Cl, while the [Au@Cu] cluster is assembled through the treatment of a pre-organized [Au(PyP)] metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions.

Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized.