A new phosphorescent heteroleptic cuprous complex with a neutral 2‐methylquinolin‐8‐ol ligand: synthesis, structure characterization, properties and TD–DFT calculations

Luminescent CuI complexes have emerged as promising substitutes for phosphorescent emitters based on Ir, Pt and Os due to their abundance and low cost. The title heteroleptic cuprous complex, [9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)‐9H‐xanthene‐κ2P,P](2‐methylquinolin‐8‐ol‐κ2N,O)copper(I) hexafluorophosphate, [Cu(C10H9NO)(C39H32OP2)]PF6, conventionally abbreviated as [Cu(Xantphos)(8‐HOXQ)]PF6, where Xantphos is the chelating diphosphine ligand 9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)‐9H‐xanthene and 8‐HOXQ is the N,O‐chelating ligand 2‐methylquinolin‐8‐ol that remains protonated at the hydroxy O atom, is described. In this complex, the asymmetric unit consists of a hexafluorophosphate anion and a whole mononuclear cation, where the CuI atom is coordinated by two P atoms from the Xantphos ligand and by the N and O atoms from the 8‐HOXQ ligand, giving rise to a tetrahedral CuP2NO coordination geometry. The electronic absorption and photoluminescence properties of this complex have been studied on as‐synthesized samples, whose purity had been determined by powder X‐ray diffraction. In the detailed TD–DFT (time‐dependent density functional theory) studies, the yellow emission appears to be derived from the inter‐ligand charge transfer and metal‐to‐ligand charge transfer (M+L′)→LCT excited state (LCT is ligand charge transfer). In the heteroleptic cuprous complex [Cu(Xantphos)(8‐HOXQ)]PF6 [Xantphos is 9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)‐9H‐xanthene and 8‐HOXQ is 2‐methylquinolin‐8‐ol], the hydroxy group of the N,O‐chelating 8‐HOXQ ligand remains protonated. TD–DFT (time‐dependent density functional theory) studies demonstrate that the yellow phosphorescence is most likely derived from the emissive (M+L′)→LCT (LCT is ligand charge transfer) excited state.