Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole

Resumo

The results of the spectroscopic NMR (¹H, ¹³C, and ¹⁹⁵Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn^–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn^–, and Dtc^– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the ¹MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.