Synthesis of Phosphorus/Arsenic Tridentate Ligands and Their Application for Luminescent Copper (I) Halide Complexes

Abstract We synthesized arsenic analogs of a tridentate PPP ligand, bis[2‐(diphenylphosphino) phenyl] phenylphosphine, achieving yields of 40 % to 71 %. Additionally, we prepared copper (I) halide (CuX, X=Br, I) complexes with these ligands, with yields between 43 % and 84 %. Using both experimental and computational methods, we examined their structures and photophysical characteristics. Single crystal X‐ray diffraction showed that all eight complexes had distorted tetrahedral geometries. These complexes exhibited photoluminescence with emission bands peaking from 506 nm to 551 nm and quantum yields up to 0.92 at room temperature. Emission lifetimes varied and showed no direct correlation with quantum yields or wavelengths. Physical manipulation and solvent variations significantly altered their photoluminescent properties. DFT and TD‐DFT calculations revealed that higher arsenic content increased spin‐orbit coupling constants, with iodide complexes performing better than bromide ones due to heavier elements enhancing spin‐orbit coupling. Substituting phosphorus with arsenic significantly affected the luminescence quantum yield and lifetime, demonstrating the heavy‐atom effect of arsenic. The position of arsenic in the ligands critically influenced the photophysical outcomes of the CuX complexes.