Assembly of silver(I)-copper(I) bimetallic thiolate complexes assisted by phenylacetylene stabilizers.

Ag/Cu bimetallic clusters have been widely reported, but synthesis of such clusters simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of Cu ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CHCN)]PF in conjunction with the (PrSAg) polymer to form Ag(I)-Cu(I) oligomer precursors, serving as the starting point for constructing a new [AgCu(PrS)(DPPM)](PF) cluster (DPPM = bis(diphenylphosphino)methane, Ag11-xCux, = 5-9). When the (PrSAg) precursor was replaced by (BuSAg), another cluster [AgCuS(BuS)(CHCN)](CHOH)(HO)(PF) (Ag21Cu4) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent Ag11-xCux were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 μs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize Cu ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions.