Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and...

Luminescent copper(I) halide complexes with bi- and tridentate rigid ligands have gained wide research interests. In this paper, six tetracoordinate dinuclear copper(I) halide complexes, Cu₂X₂(ppda)₂ [ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline, X = I (1), Br (2), Cl (3)] and Cu₂X₂(pfda)₂ [pfda = 2-[2-(dimethylamino)-4-(trifluoromethyl)phenyl(phenyl)phosphino]-N,N-dimethyl-5-trifluoromethylaniline, X = I (4), Br (5), Cl (6)], were successfully prepared and systematically characterized on their structures and photophysical properties. Complexes 1-5 have a centrosymmetric form with a planar Cu₂X₂ unit, and complex 6 has a mirror symmetry form with a butterfly-shaped Cu₂X₂. Solid complexes 1, 4, and 5 emit delayed fluorescence at room temperature, intense blue to greenish yellow (λ_max = 443-570 nm) light, and their peak wavelengths are located at 443-570 nm with microsecond lifetimes (τ = 0.4-19.2 μs, Φ_PL = 0.05-0.48). Complexes 2, 3, and 6 show prompt fluorescence, very weak yellowish green to yellow (λ_max = 534-595 nm) emission with peak wavelengths at 534-595 nm, and lifetimes in nanoseconds (τ = 4.4-9.3 ns, Φ_PL < 0.0001). (Metal + halide) to ligand and intraligand charge transitions are the main origin of the emission of the complexes. Solution-processed, complex-4-based nondoped and doped devices emit yellow green light with CIE coordinated at (0.41, 0.51), a maximum EQE up to 0.17%, and luminance reaching 75.52 cd/m².