Star-shaped multifunctional organic emitters based on N-(2-cyanophenyl) carbazole frameworks: Effects of steric hindrance fluorene and heavy-atom bromine.

To investigate the effects of steric hindrance fluorene and heavy-atom bromine on the general optoelectronic properties of star-shaped organic emitters based on 9-(2-cyanophenyl) carbazole (OCzPhCN) frameworks, heavy element of bromine and steric hindrance fluorene were introduced into OCzPhCN to produce four derivatives of 2-(3-bromo-9H-carbazol-9-yl)benzonitrile (BrCzPhCN), 2-(3-bromo-6-(9-(4-ethoxyphenyl)-9H-fluoren-9-yl)-9H-carbazol-9-yl)benzonitrile (BrFCzPhCN), 2-(3-(9-(4-ethoxyphenyl)-9H-fluoren-9-yl)-9H-carbazol-9-yl)benzonitrile (FCzPhCN) and 2-(3,6-bis(9-(4-ethoxyphenyl)-9H-fluoren-9-yl)-9H-carbazol-9-yl)benzonitrile (2FCzPhCN). The fluorene units obviously improve the thermal stability of the obtained compounds, and 2FCzPhCN has the highest thermal stability with 5 % mass heat loss temperature reaching 447 °C. In different polar solvents, the absorption peaks wavelength of OCzPhCN, FCzPhCN and 2FCzPhCN are basically unchanged, and the redshifted emission peaks are positively correlated with solvent polarity. The photoluminescence quantum yields (PLQYs) of OCzPhCN, BrCzPhCN, FCzPhCN, BrFCzPhCN and 2FCzPhCN powders were 20.17 %, 5.43 %, 30.75 %, 3.27 % and 23.56 %. The fluorescence and phosphorescent quantum efficiencies of OCzPhCN, BrCzPhCN, FCzPhCN, BrFCzPhCN and 2FCzPhCN powders are 9.76 % and 10.41 %, 1.2 % and 3.23 %, 28.45 % and 2.3 %, 3.27 % and 0 %, 23.56 % and 0 %. OCzPhCN, BrCzPhCN and FCzPhCN powders show obvious room temperature phosphorescent emission, and the phosphorescent emission lifetime of OCzPhCN, BrCzPhCN and FCzPhCN powders at 561 nm, 576 nm and 568 nm are 193.17 ms, 18.65 ms and 7.25 ms. Compared with OCzPhCN, the introduction of bromine decreases the PLQY and the phosphorescent lifetime of BrCzPhCN powder, while the fluorescence quantum efficiency of the compound FCzPhCN powder has been improved. The corresponding single-triplet energy splitting (ΔE) of OCzPhCN, FCzPhCN and 2FCzPhCN in solutions are 0.49 eV, 0.63 eV and 0.63 eV, and the corresponding ΔE values of OCzPhCN, BrCzPhCN FCzPhCN powders are 1.19 eV, 0.74 eV and 0.55 eV. The steric hindrance fluorene units result in smaller and stabilized ΔE in the solid powder states, and the same situation is opposite in the unimolecular solutions. The maximum external quantum efficiency of organic light-emitting diode based on 10,10'-(4,4'-sulfonylbis (4,1-phenylene)) bis (9,9-dimethyl-9,10-dihydroacridine) hosted by OCzPhCN reaches 12.7 %, and the external quantum efficiency at 100 cd/m rolls down to 11 %. OCzPhCN is the best emitters in terms of room temperature phosphorescent emission and host applications.