Bis‐tridentate IrIII Phosphors Bearing Two Fused Five‐Six‐Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

• Published in: Chemistry : a European journal Vol. 25; no. 67; pp. 15375 - 15386
• Main Authors: Hsu, Ling‐Yang, Liang, Qiumin, Wang, Zhiheng, Kuo, Hsin‐Hung, Tai, Wun‐Shan, Su, Shi‐Jian, Zhou, Xiuwen, Yuan, Yi, Chi, Yun
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 02.12.2019; Wiley Subscription Services, Inc
• Subjects: Angles (geometry); Bearing; Cadmium; Chelates; Chelation; Chemistry; Chemistry, Multidisciplinary; Diodes; Efficiency; Emitters; Fabrication; Iridium; Iridium compounds; ligand design; Ligands; luminescence; Organic light emitting diodes; Organometallic compounds; Phosphorescence; Phosphors; Photodegradation; Physical Sciences; Quantum efficiency; Room temperature; Science & Technology; Toluene; PLATINUM(II) COMPLEXES; NHC; POTENTIALS; organic light-emitting diodes; iridium; LIGHT-EMITTING-DIODES; MOLECULAR DESIGN; luminescence; EXTERNAL QUANTUM EFFICIENCY; IRIDIUM COMPLEXES; LIGANDS SYNTHESIS; chelates; ligand design; CONTINUUM; METAL-COMPLEXES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201903707

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light‐emitting diodes (OLEDs). In this contribution, we report a series of blue‐emitting, bis‐tridentate IrIII complexes bearing chelates with two fused five‐six‐membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five‐five metallacycles. Five IrIII complexes, Px‐21–23, Cz‐4, and Cz‐5, have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five‐five‐coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD‐DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac‐[Ir(ppy)3] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl‐functionalized emitter Cz‐5 exhibited the best performance among all the studied bis‐tridentate phosphors, showing a maximum external quantum efficiency (EQEmax) of 18.7 % and CIEx,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m−2 due to efficiency roll‐off. Seeing blue: Bis‐tridentate IrIII complexes bearing two fused five‐six‐membered metallacycles are reported herein. Both chelates possess an enlarged bite angle between the peripheral coordinating units, leading to increased emission efficiency, shortened radiative lifetime, and improved photostability for these blue emitters (see figure).