Luminescent Silver(I) and Copper(I) Systems Containing Pyridyl Phosphine Bridges

Luminescent silver(I) and copper(I) complexes containing pyridylphosphine ligands have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The reaction of Ag(OTf) (OTf = trifluoromethanesulfonate) with 2-pyridyldiphenylphosphine in different molar ratios gives the species [Ag2(OTf)2(μ-PPh2py)2] (1), [Ag(PPh2py)2]OTf (2), [Ag(PPh2py)3]OTf (3), and [Ag2(PPh2py)3](OTf)2 (4) with several modes of coordination of the pyridylphosphine. The oxidation of the phosphine in compound 4 gave [Ag2(OTf)(μ-PPh2py)2(OPPh2py)]OTf (5) which has been structurally characterized. It shows two bridging phosphine ligands and one chelating OPPh2py ligand. The reactions of the silver salt with bis(2-pyridyl)phenylphosphine in different molar ratios affords the complex [Ag2(OTf)2(μ-PPhpy2)2] (6), while the corresponding reactions with [Cu(NCMe)4]PF6 lead to two different compounds, namely [Cu2(NCMe)2(μ-PPhpy2)2](PF6)2 (7) and [Cu2(PPhpy2)2(μ-PPhpy2)2](PF6)2 (8). All complexes exhibit luminescence in the solid state at room temperature and at 77 K.