We report a new family of homoleptic iridium(III) complexes that emit blue phosphorescence at room temperature. The iridium(III) complexes are comprised of phenyltriazole ligands and were easily prepared via short synthetic routes. The parent fac-tris(1-methyl-5-phenyl-3-propyl-[1,2,4]triazolyl)iridium(III) complex exhibits blue photoluminescence (PL) with emission peaks at 449 and 479 nm and has a solution PL quantum yield of 66%. The emission was sequentially blue-shifted by the attachment of one and two fluorine atoms to the ligand phenyl ring with the fac-tris{1-methyl-5-(4,6-difluorophenyl)-3-propyl-[1,2,4]triazolyl}iridium(III) complex having the 1931 Commission Internationale de l'Eclairage coordinates of (0.16, 0.12) at room temperature. In contrast, when the phenyl ring of the ligands was substituted by trifluoromethyl, the PL spectrum was red-shifted when compared to the parent compound whereas if the trifluoromethyl group was attached to the triazole ring, the emission was blue-shifted. The radiative rates of these new blue iridium(III) complexes were found to be in the range of 2−6 × 105 s-1, indicating that the emission had varying amounts of metal-to-ligand charge-transfer character. Molecular orbital calculations showed that for the fluorinated complexes the contribution of the ligand triplet character to the emissive energy state increased with the hypsochromic shift in emission. This was confirmed by time-resolved PL measurements, which showed that the complex with the deepest blue emission had the slowest radiative decay rate.
Solution‐processible saturated blue phosphorescence is an important goal for organic light‐emitting diodes (OLEDs). Fac‐tris(5‐aryltriazolyl)iridium(III) complexes can emit blue phosphorescence at room temperature. Mono‐ and doubly dendronized fac‐tris(1‐methyl‐5‐phenyl‐3‐n‐propyl‐1H‐[1,2,4]triazolyl)iridium(III) 1 and fac‐tris{1‐methyl‐5‐(4‐fluorophenyl)‐3‐n‐propyl‐1H‐[1,2,4]triazolyl}iridium(III) 4 with first generation biphenyl‐based dendrons were prepared. The dendrimers emitted blue light at room temperature and could be solution processed to form thin films. The doubly dendronized 3 had a film photoluminescence quantum yield of 67% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.17, 0.33). OLEDs comprised of a neat film of dendrimer 3 and an electron transport layer achieved a brightness of 142 cd m−2 at 3.8 V with an external quantum efficiency of 7.9%, and CIE coordinates of (0.18, 0.35). Attachment of the fluorine atom to the emissive core had the effect of moving the luminescence to shorter wavelengths but also quenched the luminescence of the mono‐ and doubly dendronized dendrimers.
Solution-processable blue phosphorescent emitters with high luminescence efficiency are highly desirable for large-area displays and lighting applications. This report shows that when a fac-tris[1-methyl-5-(4-fluorophenyl)-3-n-propyl-1H-[1,2,4]triazolyl]iridium(III) complex core is encapsulated by rigid high-triplet-energy dendrons, both the physical and photophysical properties can be optimized. The high-triplet-energy and rigid dendrons were composed of twisted biphenyl dendrons with the twisting arising from the use of tetrasubstituted branching phenyl rings. The blue phosphorescent dendrimer was synthesized using a convergent approach and was found to be solution-processable and to possess a high glass transition temperature of 148 degrees C. The dendrimer had an exceptionally high solution photoluminescence quantum yield (PLQY) of 94%, which was more than three times that of the simple parent core complex (27%). The rigid and high-triplet-energy dendrons were also found to control the intermolecular interactions that lead to the quenching of the luminescence in the solid state, and the film PLQY was found to be 60% with the emission having Commission Internationale de l'Eclairage coordinates of (0.16, 0.16). The results demonstrate that dendronization of simple chromophores can enhance their properties. Single layer neat dendrimer organic light-emitting diodes (OLEDs) had an external quantum efficiency (EQE) of 0.4% at 100 cd/m(2). Bilayer devices with an electron transport layer gave improved EQEs of up to 3.9%. Time-resolved luminescence measurements suggest that quenching of triplets by the electron transport layer used in the bilayer OLEDs limits performance.
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