Green Ir(III) complexes with multifunctional ancillary ligands for highly efficient solution-processed phosphorescence organic light-emitting diodes with high current efficiency

Two new highly efficient green emitting heteroleptic Ir(III) complexes, namely, bis[5-(2-ethylhexyl)-8-(trifluoromethyl)benzo[c][1,5]naphthyridin-6(5H)-one]iridium-4-((3,5-di(9H-carbazol-9-yl)benzyl)oxy)picolinate (Ir-HT) and bis[5-(2-ethylhexyl)-8-(trifluoromethyl) benzo[c][1,5]naphthayridin-6(5H)-one]iridium-4-((4-(5-phenyl-1,3,4-oxadiazol-2-yl)benzyl) oxy)picolinate (Ir-ET) were designed and synthesized for solution-processed phosphorescence organic light-emitting diodes (PHOLEDs). These new Ir(III) complexes are based on amide-bridged trifluoromethyl (-CF₃) substituted phenylpyridine unit as main ligand and 1,3-bis(N-carbazolyl)benzene (mCP) unit and 1,3,4-oxadiazole (OXD) unit functionalized picolinate (pic) as an ancillary ligand. These multifunctional groups were attached into the 4-position of pic ancillary ligands via ether linkage. Interestingly, the solution-processed PHOLED device using Ir-HT as a dopant exhibited a maximum external quantum efficiency (EQE_max) of 20.92% and a maximum current efficiency (CE_max) of 64.04 cd A⁻¹. Whereas PHOLED device using Ir-ET displayed a EQE_max of 20.68% and a CE_max of 65.02 cd A⁻¹. This is one of best CE with high EQE for green Ir(III) complexes via solution-processed PHOLEDs using multifunctional ancillary ligands so far.     

A green emitting iridium(III) complex with narrow emission band and its application to phosphorescence organic light-emitting diodes (OLEDs)

The homoleptic Ir(III) complex, fac-tris{2-(3′-trimethylsilylphenyl)-5-trimethylsilylpyridinato}iridium, has been synthesized and characterized to investigate the effect of the substitution of bulky silyl groups on the photophysical properties and electroluminescence (EL) characteristics of Ir(ppy)₃ (ppy = 2-phenylpyridine). The absorption, emission, cyclic voltammetry and electroluminescent performance of the complex have also been evaluated. A power efficiency of 17.3 lm/W at 10 mA/cm² compared to 11.7 lm/W for Ir(ppy)₃ is achieved with the new complex as a dopant in phosphorescent organic light-emitting diodes (OLEDs). In addition, the complex shows a narrow emission band of a small full width at half-maximum (fwhm, ca. 50 nm) value.     

Simple molecular structure design of iridium(III) complexes: Achieving highly efficient non-doped devices with low efficiency roll-off

To construct efficient emitters suitable for non-doped devices and deeply understand the relationship between structures and performances, we designed and synthesized two heteroleptic iridium(III) complexes based on 1,2-diphenyl-1H-benzoimidazole (PBI) ligands whose substituents are varied simply from methyl (complex 2) to tert-butyl groups (complex 3). The parent complex 1 with non-substituent on PBI ligand has also been presented for a better comparison. Their photophysical, electrochemical and electroluminescent (EL) performances are investigated systematically. Despite their structural modification, all complexes exhibit almost identical emission and excited-state characters, which are rationalized by the quantum-chemical calculations. However, the obvious differences on device performances are found. Non-doped device employing 3 as emitting layer displays the highest EL performance with maximum current efficiency (η_{c, max}) of 18.6 cd A⁻¹ and power efficiency (η_{p, max}) of 16.2 lm W⁻¹ accompanied by low efficiency roll-off values, which is much higher than those of complexes 1 and 2. The obtained results herein suggest that introduction of the simple substituent into PBI ligand is an effective and feasible approach to develop highly efficient non-doped phosphors.     

Heteroleptic iridium (III) complexes with three different ligands: Unusual triplet emitters for light-emitting electrochemical cells

Two cationic iridium (III) complexes [Ir(dfppy)(tpy)(bpy)](PF₆) and [Ir(dfppy)(tpy)(phen)](PF₆) bearing three different ligands were tested as triplet emitters for Light-Emitting Electrochemical Cells (LECs). These two phosphorescent materials only constitute the third and fourth examples of triple heteroleptic cationic iridium complexes to be tested in electroluminescent devices. LECs fabricated with this almost unknown class of iridium complex furnished green-emitting devices. Parallel to investigations devoted to electroluminescent properties, photophysical and electrochemical properties of the two new complexes were examined. Density functional theory calculations were also performed to provide insight into the electronic structure of the two emitters.     

Tuning the color and phosphorescent properties of iridium(III) complexes with phosphine-silanolate ancillary ligand: A theoretical investigation

A series of Ir(III) complexes [(CˆN)₂Ir(PˆSiO)], where (CˆN)H is 2-phenylisoquinoline (1), 2-phenylpyridine (2) or 2-(2,4-difluorophenyl)pyridine (3), and (PˆSiO)H is an organosilanolate ancillary chelate with either diphenylsilyl (a) or dimethylsilyl (b) substituent, are investigated by means of the density functional theory/time-dependent density functional theory (DFT/TD-DFT). Their relationship between structure and property is evaluated by the geometries, electronic structure, and absorption and phosphorescence spectra associated with the internal quantum yield. The effect of different substitutions on the ancillary ligand is explored by compare of the complexes 1a (2a/3a) and 1b (2b/3b). Furthermore, five complexes, 2b-1, 2b-2, 2b-3, 2b-4, and 2b-5, are newly designed by introduction of the substitution groups on the phenyl rings of the 2b (See Fig. 1). The theoretical result estimates that the complexes 2b-1, 2b-2, 2b-4, and 2b-5 would be the blue-emitting phosphors. Especially, the complex 2b-1 has a higher quantum yield relative to 2b by comparison of the factors governing the radiative decay rate constants of the emissive state and the feasibility of the deactivation process from the T₁ state via triplet metal-centered (³MC) state.     

Two novel orange cationic iridium(III) complexes with multifunctional ancillary ligands used for polymer light-emitting diodes

Two novel orange cationic iridium complexes [(npy)₂Ir(o-phen)]PF₆ and [(npy)₂Ir(c-phen)]PF₆ were synthesized. Hnpy: 2-(naphthalen-1-yl)pyridine; o-phen: a 1,10-phenanthroline derivative containing an electron-transporting functional group of 2,5-diphenyl-1,3,4-oxadiazole and a crystallization-resistant tert-butyl functional group; c-phen: a 1,10-phenanthroline derivative containing a hole-transporting functional group of carbazole and a crystallization-resistant 2-ethylhexyl functional group. Both of them are amorphous and possess high thermal stability with 5% weight-reduction temperatures (ΔT_5%) of 386 °C and 383 °C, and glass-transition temperatures (T_g) of 267 °C and 195 °C respectively. They were used as phosphorescent dopants in polymer light-emitting diodes (PLEDs) fabricated by solution-processed technology with configuration of ITO/PEDOT:PSS/PVK:PBD:iridium complex/TPBI/CsF/Al. At the optimal doping concentration of 2.0 wt%, the corresponding PLEDs exhibited the maximum current efficiencies of 9.1 cd A⁻¹ and 10.0 cd A⁻¹, the maximum external quantum efficiencies of 6.5% and 7.1%, and the maximum luminance of 2314 cd m⁻² and 3157 cd m⁻² respectively, with the same CIE coordinates of (0.57, 0.40). The results indicate that cationic iridium complexes are promising candidates for PLED applications when they are designed reasonably.     

A theoretical study of phosphorescent Cu(I) complexes with 2-(2'quinolyl)imidazole and POP mixed ligands

We herein report a theoretical study using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods to investigate Cu(I) complexes with 2-(2′-pyridyl/quinolyl)imidazole and bis[2-(diphenylphosphino)phenyl]ether mixed ligands. Based on the experimental data for complexes 1 and 2, we first benchmarked different functionals with different HF% and found B3PW91 to be the optimal functional for this system. The computational results indicate that complex 1, with a pyridyl unit, has a much larger radiative decay rate (k_r) than complex 2, which has a quinolyl unit. This difference is presumably due to higher HOMO electronic distribution in the d_x²-_y² orbital, which leads to a markedly shortened CuN₂ bond, enhancing the metal-ligand interaction. However, a much smaller experimental value was found for the non-radiative decay rate (k_nr) in complex 2, rendering 1 a slightly weaker emitter than 2. We conclude that the difference is due to more effective suppression of deformation when the quinolyl unit is used instead of pyridyl. We sought to increase the photoluminescence quantum yield (PLQY) through modifying the ligand on complex 2, with the goal being to keep the small k_nr value while simultaneously increasing k_r. The computational results indicate that our designed complexes 2a-2c, which possess modified ligands with electron-donating or withdrawing alkyl substituents on N₃, increased the distributions of d_x²-_y² and decreased that of the d_yz compared to 2. Their coordinating abilities were therefore enhanced, with the k_r values being 1.34, 22.70, and 0.16 times that of 2 for 2a, 2b and 2c, respectively. Higher PLQYs were achieved in 2a and 2b with the addition of electron-donating alkyl substituents on the ligands, which yielded complexes with significantly shortened CuN₂ bonds and enhanced metal-ligand interaction. This investigation on the microscopic mechanism of the photoluminescent properties of these complexes can provide useful knowledge for experimentalists.     

Synthesis and characterization of blue-emitting Ir(III) complexes with multi-functional ancillary ligands for solution-processed phosphorescent organic light-emitting diodes

A series of Ir(III) complexes, (dfpmpy)₂Ir(pic), (dfpmpy)₂Ir(EO₂-pic), (dfpmpy)₂Ir(pic-N-O), and (dfpmpy)₂Ir(EO₂-pic-N-O), containing 2-(2,4-difluorophenyl)-4-methylpyridine (dfpmpy) based main ligand with varying ancillary ligands such as picolinic acid (pic), 4-(2-ethoxyethoxy)picolinic acid (EO₂-pic), picolinic acid N-oxide (pic-N-O), and 4-(2-ethoxyethoxy)picolinic acid N-oxide (EO₂-pic-N-O), respectively were successfully synthesized for highly efficient blue phosphorescent organic light-emitting diodes (PhOLEDs). The photophysical, electrochemical, and electroluminescent (EL) properties were systematically correlated. The solubilizing 2-ethoxyethanol (EO₂-) group was attached to the ancillary ligand through tandem reaction. All of the Ir(III) complexes show high thermal stability and good photoluminescence quantum yields (Ф_pl) in film state. Solution-processed PhOLEDs were fabricated using these Ir(III) complexes as dopants and achieved a maximum external quantum efficiency (EQE) of 10.9% and current efficiency of 21.15 cd/A for (dfpmpy)₂Ir(EO₂-pic). All the Ir(III) complexes emitted blue light with color purity at the Commission Internationale de L’Eclairage (CIE) coordinates of (0.15, 0.31).     

Theoretical perspective for internal quantum efficiency of thermally activated delayed fluorescence emitter in solid phase: A QM/MM study

Excited state dynamics and charge transfer property of an orange-red thermally activated delayed fluorescence (TADF) emitter are theoretically investigated by a quantum mechanics/molecular mechanics (QM/MM) method and kinetic Monte Carlo simulation. The factors that influence internal quantum efficiency of the organic light-emitting diode (OLED) based on an asymmetric donor–acceptor (D–A) type molecule 10-(7-fluoro-2,3-diphenylquinoxalin-6-yl)-10H-phenoxazine (FDQPXZ) are analyzed. The results show that the intramolecular rotation of donor unit is restricted because of the enhanced intermolecular interaction in solid phase, which hinders the non-radiative consumption of the excited state energy. The decreased reorganization energy in solid phase is mainly contributed by dihedral angle in low-frequency (<500 cm⁻¹) region. Moreover, the non-radiative decay rate from the first singlet excited state (S1) to the ground state (S0) in solid phase is shown to be smaller than that in gas phase. In order to explore the charge transfer process in the film of FDQPXZ, Marcus theory is used to study the hole and electron transfer rates, and the charge mobility is thus obtained by Monte Carlo simulation. The theoretical calculation indicates that the FDQPXZ film is a p-type organic molecular material under the hopping mechanism. Intermolecular interaction for theoretical simulation of the working principle of OLEDs is highlighted.