A series of silver(I) complexes with bis[2-(diphenylphosphino)phenyl]ether (DPEphos) and bis(diphenylphosphino)ethane (dppe): Synthesis, structural characterization and photophysical properties

Abstract

Eight silver(I) complexes containing DPEphos (bis[2-(diphenylphosphino)phenyl]ether) and dppe (bis(diphenylphosphino)ethane), namely [Ag2Cl2(DPEphos)2(dppe)](CH3OH)2(DMF) (1), [Ag2Br2(DPEphos)2](DMF)2 (2), [Ag2(OTf)2(DPEphos)2(dppe)] (3) (OTf=trifluoromethanesulfonate), [Ag2(NO3)2(DPEphos)2(dppe)] (4), [Ag(DPEphos)(dppe)](OTf) (5), [Ag(NO3)(DPEphos)] (6), [Ag(NO2)(DPEphos)] (7) and [Ag(DPEphos)(dppe)](BF4) (8), have been synthesized. They were characterized by IR spectroscopy, X-ray diffraction, RT luminescence, 1H and 31P NMR spectroscopy. Complexes 5–8 were obtained in the mixed solvents of CH3OH and CH2Cl2, while 1–4 were obtained in the mixed solvents of CH3OH, CH2Cl2 and DMF (DMF=N,N-dimethylformamide). Complexes 1–4 display dinuclear structures, in which two silver atoms are bridged by one dppe ligand (for 1, 3 and 4) or two Br atoms (for 2). The other four are mononuclear complexes. The 31P NMR spectra of the title compounds are measured, each spectrum shows rich signals which belong to P atoms in different chemical environment. In the 31P NMR spectra, there exist splitting signals (doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P or 19F–31P, where the coupling of 19F–31P was found for the first time in silver(I)–P complexes containing OTf− or BF4− anions.