Heterometallic Au(I)–Cu(I) Clusters: Luminescence Studies and (1)O(2) Production

[Image: see text] Two different organometallic gold(I) compounds containing naphthalene and phenanthrene as fluorophores and 2-pyridyldiphenylphosphane as the ancillary ligand were synthesized (compounds 1 with naphthalene and 2 with phenanthrene). They were reacted with three different copper(I) salts with different counterions (PF(6)(–), OTf(–), and BF(4)(–); OTf = triflate) to obtain six Au(I)/Cu(I) heterometallic clusters (compounds 1a–c for naphthalene derivatives and 2a–c for phenanthrene derivatives). The heterometallic compounds present red pure room-temperature phosphorescence in both solution, the solid state, and air-equilibrated samples, as a difference with the dual emission recorded for the gold(I) precursors 1 and 2. The presence of Au(I)–Cu(I) metallophilic contacts has been identified using single-crystal X-ray diffraction structure resolution of two of the compounds, which play a direct role in the resulting red-shifted emission with respect to the gold(I) homometallic precursors. Polystyrene (PS) and poly(methyl methacrylate) (PMMA) polymeric matrices were doped with our luminescent compounds, and the resulting changes in their emissive properties were analyzed and compared with those previously recorded in the solution and the solid state. All complexes were tested to analyze their ability to produce (1)O(2) and present very good values of Φ(Δ) up to 50%.