Coinage metal(I) clusters supported by a 1,10-phenanthroline-phosphine: orange-to-NIR phosphorescence, metallophilic interactions and enhanced cytotoxicity.

A series of small coinage metal(I) clusters has been selectively synthesized using 2-(diphenylphosphino)-1,10-phenanthroline (L), a new promising dimetal-binding P,N,N′-ligand (L). Its reaction with CuI yields the complex [Cu2L2(μ2-I)]2[Cu2I4], while the treatment of L with Au(tht)Cl/Ag+ or Au(tht)Cl/Cu+ systems leads to the assembly of [Au2AgL2Cl2]+, [Au2CuL2Cl2]+, [CuAuL2]2+ and [AgAuL2]2+ clusters. Theoretical analysis revealed pronounced intermetallic close shell interactions in these di- and trinuclear ensembles. At 298 K, the title compounds exhibit an orange and near-infrared (NIR) phosphorescence with lifetimes of 0.344–38 μs and quantum efficiencies of 1–21%. Theoretical considerations suggest a 3(M+L)LCT type for the observed phosphorescence. In addition, the above clusters exhibit a strong dose-dependent cytotoxic effect on A549, HepG2, Hep2 and MRC5 human cells with IC50 values ranging from 1.26 to 11.1 μM. [ABSTRACT FROM AUTHOR]