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

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 (λmax = 443-570 nm) light, and their peak wavelengths are located at 443-570 nm with microsecond lifetimes (τ = 0.4-19.2 µs, ΦPL = 0.05-0.48). Complexes 2, 3, and 6 show prompt fluorescence, very weak yellowish green to yellow (λmax = 534-595 nm) emission with peak wavelengths at 534-595 nm, and lifetimes in nanoseconds (τ = 4.4-9.3 ns, ΦPL < 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.

From a blue to white to yellow emitter: a hexanuclear copper iodide nanocluster.

Highly emissive copper(i) halide nanoclusters showing thermally activated delayed fluorescence (TADF) have been paid much attention, but rarely reported so far. Herein, a hexanuclear copper(i) iodide cluster containing a tridentate N∧P∧N ligand, [Cu6I6(ppda)2] {ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline}, was synthesized. All six copper atoms are four-coordinate, including four CuPNI2 and two CuI4 units. This complex exhibits intense white emission in the powder state at room temperature and shows a peak at a wavelength of 535 nm (ΦPL = 0.36) with a microsecond lifetime (τ = 4.4 µs). Emission colors can be largely tuned from blue to white to yellow, from the crystal to powder to film state at 297 K. The emission of [Cu6I6(ppda)2] originates from a combination of MLCT and XLCT transitions. This complex showed good thermal stability. A solution-processed, nondoped device of complex [Cu6I6(ppda)2] exhibits stable yellow emission with the CIE coordinates (x, y) of (0.43, 0.51). [Cu6I6(ppda)2] also shows reasonable photocatalytic H2 evolution activity under visible-light irradiation.