Syntheses, Photoluminescence, and Electroluminescence of a Series of Sublimable Bipolar Cationic Cuprous Complexes with Thermally Activated Delayed Fluorescence.

Three thermally activated delayed fluorescence cationic cuprous complexes [Cu(POP) (ECAF)]PF6 (1, POP = bis(2-diphenylphosphinophenyl)ether, ECAF = 9,9-bis(9-ethylcarbazol-3-yl)-4,5-diazafluorene), [Cu(POP) (EHCAF)]PF6 (2, EHCAF = 9,9-bis(9-ethylhexylcarbazol-3-yl)-4,5-diazafluorene), and [Cu(POP) (PCAF)]PF6 (3, PCAF = 9,9-bis(9-phenylcarbazaol-3-yl)-4,5-diazafluorene) with bipolar 4,5-diazafluorene ligand substituted by bis-carbazole have been successfully prepared, and their UV absorption, photoluminescent properties, and electrochemical behaviors were investigated. At room temperature, complexes 1, 2, and 3 exhibit efficient yellowish-green emission with peak maxima of 550, 549, and 556 nm, respectively, and lifetimes of 5.7 μs. In powder states, the quantum yields (ϕPL) of 22.4% for 1, 18.5% for 2, and 20.0% for 3, respectively, are found. These metal phosphors can be vacuum-evaporated and applied in the organic light-emitting diodes (OLEDs) of indium tin oxide/poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (40 nm)/4,4',4″-tri(9-carbazoyl)triphenylamine (15 nm)/cuprous complexes (10 wt %): 1,3-bis(9-carbazolyl)benzene (30 nm)/1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (50 nm)/LiF (0.5 nm)/Al (100 nm). Complex 1-based device D1 achieved a maximum luminance of 11 010 cd m-2, a current efficiency of 47.03 cd A-1, and an external quantum efficiency of 14.81%. The high electroluminescence efficiencies of these complexes are assumed to be due to their good thermal stabilities and capture of both singlet and triplet excitons. The research presented here provides a powerful tool toward highly efficient and cheap OLED devices.