TY - JOUR
T1 - Excited-State Modification of Phenylimidazole-Based Cyclometalated Ir(III) Complexes through Secondary Bulky Aryl Substitution and Inductive Modification Enhances the Blue Emission Efficiency in Phosphorescent OLEDs
AU - Kim, So Yoen
AU - Kim, Jin Hyoung
AU - Lee, Sanghun
AU - Yun, Bo Sun
AU - Son, Ho Jin
AU - Kang, Sang Ook
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/11/21
Y1 - 2022/11/21
N2 - To elucidate the key parameters governing the emission properties of phenylimidazole (pim)-based Ir(III) emitters, including their electronic structure and the bulky aryl substitution effect, a series of pim-based iridium(III) complexes (Ir(Rpim-X)3 Rpim-X = 1-R-2-(X-phenyl)-1H-imidazole) bearing secondary pendants of increasing bulkiness [R = methyl (Me), phenyl (Ph), terphenyl (TPh), or 4-isopropyl terphenyl (ITPh)] and three different primary pim ligands (X = F, F2, and CN) were designed and synthesized. Based on photophysical and electrochemical analyses, it was found that the excited state properties are highly dependent on the bulkiness of the secondary substituent and the inductive nature of the primary pim ligand. The incorporation of bulky TPh/ITPh substituents in the second coordination sphere significantly enhanced the emission efficiencies in the solid state (φPL= 72.1-84.9%) compared to those of the methyl-or phenyl-substituted Ir(III) complexes (φPL= 30.4% for Ir(Mepim)3and 63.7% for Ir(Phpim)3). Further modification of the secondary aryl substituent (Ir(TPhpim)3→ Ir(ITPhpim)3) through the incorporation of an isopropyl group and F substitution on the primary pim ligand (Ir(TPh/ITPhpim)3→ Ir(TPh/ITPhpim-F/F2)3) resulted in a slight decrease in the LUMO and a significant decrease in the HOMO energy levels, respectively; these energy level adjustments consequently amplified emission blue shifts, thereby enabling efficient blue electroluminescence in phosphorescent organic light-emitting diodes. Theoretical calculations revealed that the excited-state properties of pim-based Ir(III) complexes can be modulated by the nature of the peripheral substituent and the presence of an EWG substituent. Among the fabricated blue-emitting TPh/ITPh-substituted Ir(III) complexes, Ir(ITPhpim-F)3, Ir(TPhpim-F2)3, and Ir(ITPhpim-F2)3were tested as blue-emitting dopants for blue phosphorescent OLEDs owing to their high solid radiative quantum yields (φPL= 75.9-84.9%). The Ir(ITPhpim-F)3-doped multilayer device displayed the best performance with a maximum external quantum efficiency of 21.0%, a maximum current efficiency of 43.6 cd/A, and CIE coordinates of 0.18 and 0.31.
AB - To elucidate the key parameters governing the emission properties of phenylimidazole (pim)-based Ir(III) emitters, including their electronic structure and the bulky aryl substitution effect, a series of pim-based iridium(III) complexes (Ir(Rpim-X)3 Rpim-X = 1-R-2-(X-phenyl)-1H-imidazole) bearing secondary pendants of increasing bulkiness [R = methyl (Me), phenyl (Ph), terphenyl (TPh), or 4-isopropyl terphenyl (ITPh)] and three different primary pim ligands (X = F, F2, and CN) were designed and synthesized. Based on photophysical and electrochemical analyses, it was found that the excited state properties are highly dependent on the bulkiness of the secondary substituent and the inductive nature of the primary pim ligand. The incorporation of bulky TPh/ITPh substituents in the second coordination sphere significantly enhanced the emission efficiencies in the solid state (φPL= 72.1-84.9%) compared to those of the methyl-or phenyl-substituted Ir(III) complexes (φPL= 30.4% for Ir(Mepim)3and 63.7% for Ir(Phpim)3). Further modification of the secondary aryl substituent (Ir(TPhpim)3→ Ir(ITPhpim)3) through the incorporation of an isopropyl group and F substitution on the primary pim ligand (Ir(TPh/ITPhpim)3→ Ir(TPh/ITPhpim-F/F2)3) resulted in a slight decrease in the LUMO and a significant decrease in the HOMO energy levels, respectively; these energy level adjustments consequently amplified emission blue shifts, thereby enabling efficient blue electroluminescence in phosphorescent organic light-emitting diodes. Theoretical calculations revealed that the excited-state properties of pim-based Ir(III) complexes can be modulated by the nature of the peripheral substituent and the presence of an EWG substituent. Among the fabricated blue-emitting TPh/ITPh-substituted Ir(III) complexes, Ir(ITPhpim-F)3, Ir(TPhpim-F2)3, and Ir(ITPhpim-F2)3were tested as blue-emitting dopants for blue phosphorescent OLEDs owing to their high solid radiative quantum yields (φPL= 75.9-84.9%). The Ir(ITPhpim-F)3-doped multilayer device displayed the best performance with a maximum external quantum efficiency of 21.0%, a maximum current efficiency of 43.6 cd/A, and CIE coordinates of 0.18 and 0.31.
UR - https://www.scopus.com/pages/publications/85141968879
U2 - 10.1021/acs.inorgchem.2c02890
DO - 10.1021/acs.inorgchem.2c02890
M3 - Article
C2 - 36346993
AN - SCOPUS:85141968879
SN - 0020-1669
VL - 61
SP - 18554
EP - 18567
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 46
ER -