Structure, fluorescence, redox properties and theoretical interpretation of heteroleptic copper(I) and silver(I) complexes of N-[(2-pyridyl) methyliden]-6-coumarin and triphenylphosphine

摘要

[MX(L)(PPh_3)] (L = N-[(2-pyridyl)methyliden]-6-coumarin; M = Cu(I), Ag(I); X = Cl, Br, I, N_3, SCN) are characterized by spectroscopic data. The X-ray structure of [CuCl(L)(PPh_3)] shows CuN_2PCl distorted tetrahedral coordination (L acts N,N chelator). The complexes show emission and the emission efficiency is dependent on nature of M and X; Cu(I) complexes (d~(10)) are more emissive than Ag(I) complexes which may be due to heavy atom effect of silver. [Cu(SCN)(L)(PPh_3)] shows highest emission intensity in the series. The cyclic voltammogram of [CuX(L)(PPh_3)] shows Cu(II)/Cu(I) quasireversible redox couple while[AgX(L)(PPh_3)] exhibits deposition of Ag(0) on the electrode surface together with irreversible ligand reduction. Coulometric oxidation of [CuX(L)(PPh_3)] has synthesised copper(II) derivatives. Theoretical calculations are applied in modelling of complexes studied and UV–Vis spectra simulation.