The synthesis of cyclometalated platinum(II) complexes with benzoaryl-pyridines as C

A series of (C^N)Pt(acac)-type complexes has been successfully synthesized with a benzo[b]furan, benzo[b]thiophene, benzo[b]selenophene, or benzo[b]tellurophene group in the benzoaryl-pyridine ligand. Using X-ray crystallography, the chemical structures of the complexes with benzo[b]selenophene and benzo[b]tellurophene groups have been clearly revealed. The photophysical, electrochemical, and electroluminescent (EL) behaviors of these (C^N)Pt(acac)-type complexes have been fully characterized. Furthermore, both time-dependent functional theory (TD-DFT) and natural transition orbital (NTO) theoretical results have been obtained to gain insight into the absorption and emission features. It has been shown that both the absorption bands with the lowest energy and the phosphorescence emission behaviors are dominated by the benzoaryl-pyridine cyclometalating ligand. Importantly, the effects of the group VIA atoms on the properties of these (C^N)Pt(acac)-type complexes have been revealed. Owing to the rareness of (C^N)Pt(acac)-type complexes with benzo[b]selenophene and benzo[b]tellurophene groups, their EL abilities have been characterized using solution-processed organic light-emitting diodes (OLEDs). The optimized red OLEDs with the complex bearing a benzo[b]selenophene unit show a maximum external quantum efficiency (ηext) of 6.3%, current efficiency (ηL) of 10.5 cd A-1, and power efficiency (ηP) of 9.1 lm W-1, while the EL device with the complex bearing a benzo[b]tellurophene unit can give deep-red emission at ca. 636 nm with ηext of 6.3%, ηL of 6.5 cd A-1, and ηP of 5.8 lm W-1. This research not only provides novel (C^N)Pt(acac)-type complexes, but also furnishes critical information regarding the photophysical and EL behavior of these new complexes.

Highly Efficient Deep-Red Organic Light-Emitting Devices Based on Asymmetric Iridium(III) Complexes with the Thianthrene 5,5,10,10-Tetraoxide Moiety.

Highly efficient deep-red organic light-emitting devices (OLEDs) are indispensable for developing high-performance red-green-blue (RGB) displays and white OLEDs (WOLEDs). However, the shortage of deep-red emitters with high photoluminescence quantum yields (PLQYs) and balanced charge injection/transport abilities has severely restricted the performance of deep-red OLEDs. Herein, we design and synthesize four efficient emitters by combining the isoquinoline group with the thianthrene 5,5,10,10-tetraoxide group. Benefited from the introduction of the thianthrene 5,5,10,10-tetraoxide group, these Ir(III) complexes show improved electron-injection/-transport abilities. By enhancing the contribution of the triplet metal-to-ligand charge transfer (3MLCT) in emissions, the asymmetric configuration endows the related deep-red Ir(III) complexes with high PLQYs of 0.45-0.50 in solutions. More importantly, PLQYs of these Ir(III) complexes in doped host films increase up to 0.91, which is much higher than PLQYs reported for conventional deep-red Ir(III) complexes with impressive electroluminescent performance. As a result, solution-processed OLEDs based on these Ir(III) complexes exhibit deep-red emissions with Commission Internationale de L'Eclairage (CIE x, y) coordinates very close to the National Television System Committee (NTSC)-recommended standard red CIE coordinates of (0.67, 0.33). Furthermore, a deep-red OLED using the asymmetric Ir(III) complex SOIrOPh as the emitter shows outstanding performance with a peak external quantum efficiency (EQE) of 25.8%, which is the highest EQE reported for solution-processed deep-red OLEDs. This work sheds light on the great potential of utilizing the thianthrene 5,5,10,10-tetraoxide group to develop phosphorescent emitters for highly efficient OLEDs.

Asymmetric Heteroleptic Ir(III) Phosphorescent Complexes with Aromatic Selenide and Selenophene Groups: Synthesis and Photophysical, Electrochemical, and Electrophosphorescent Behaviors.

With the aim of evaluating the potential of selenium-containing groups in developing electroluminescent (EL) materials, a series of asymmetric heteroleptic Ir(III) phosphorescent complexes (Ir-Se0F, Ir-Se1F, Ir-Se2F, and Ir-Se3F) have been synthesized by using 2-selenophenylpyridine and one ppy-type (ppy = 2-phenylpyridine) ligand with a fluorinated selenide group. To the best of our knowledge, these complexes represent unprecedented examples of asymmetric heteroleptic Ir(III) phosphorescent emitters bearing selenium-containing groups. Natural transition orbital (NTO) analysis based on optimized geometries of the first triplet state (T1) have shown that the phosphorescent emissions of these Ir(III) complexes dominantly show 3π-π* features of the 2-selenophenylpyridine ligand with slight metal to ligand charge transfer (MLCT) contribution. In comparison with their symmetric parent complex Ir-Se with two 2-selenophenylpyridine ligands, these asymmetric heteroleptic Ir(III) phosphorescent complexes can show much higher phosphorescent quantum yields (ΦP) of ca. 0.90. Both the hole- and electron-trapping ability of these Ir(III) phosphorescent complexes can be enhanced by selenophene and fluorinated selenide groups to improve their EL efficiencies. The EL abilities of these asymmetric heteroleptic Ir(III) phosphorescent emitters fall in the order Ir-Se3F > Ir-Se2F > Ir-Se1F > Ir-Se0F. The highest EL efficiencies have been achieved by Ir-Se3F in the solution-processed OLEDs with external quantum efficiency (ηext), current efficiency (ηL), and power efficiency (ηP) of 19.9%, 65.6 cd A-1, and 57.3 lm W-1, respectively. These encouraging EL results clearly indicate the great potential of selenium-containing groups in developing high-performance Ir(III) phosphorescent emitters.

Erratum: Diarylboron-Based Asymmetric Red-Emitting Ir(III) Complex for Solution-Processed Phosphorescent Organic Light-Emitting Diode with External Quantum Efficiency above 28.

[This corrects the article DOI: 10.1002/advs.201701067.].

Diarylboron-Based Asymmetric Red-Emitting Ir(III) Complex for Solution-Processed Phosphorescent Organic Light-Emitting Diode with External Quantum Efficiency above 28.

Organic light-emitting diodes (OLEDs) are one of the most promising technologies for future displays and lighting. Compared with the blue and green OLEDs that have achieved very high efficiencies by using phosphorescent Ir(III) complexes, the red OLEDs still show relatively low efficiencies because of the lack of high-performance red-emitting Ir(III) complexes. Here, three highly efficient asymmetric red-emitting Ir(III) complexes with two different cyclometalating ligands made by incorporating only one electron-deficient triarylboron group into the nitrogen heterocyclic ring are reported. These complexes show enhanced photoluminescence quantum yields up to 0.96 and improved electron transporting capacity. In addition, the asymmetric structure can help to improve the solubility of Ir(III) complexes, which is crucial for fabricating OLEDs using the solution method. The photoluminescent and oxidation-reduction properties of these Ir(III) complexes are investigated both experimentally and theoretically. Most importantly, a solution-processed red OLED achieves extremely high external quantum efficiency, current efficiency, and power efficiency with values of 28.5%, 54.4 cd A-1, and 50.1 lm W-1, respectively, with very low efficiency roll-off. Additionally, the related device has a significantly extended operating lifetime compared with the reference device. These results demonstrate that the asymmetric diarylboron-based Ir(III) complexes have great potential for fabricating high-performance red OLEDs.

Highly efficient electroluminescent PtII ppy-type complexes with monodentate ligands.

Functional PtII ppy-type complexes (ppy = 2-phenylpyridine anion) with pyridine and chloride monodentate ligands are prepared, which show high electroluminescence efficiencies.

Bis-ZnII salphen complexes bearing pyridyl functionalized ligands for efficient organic light-emitting diodes (OLEDs).

Inspired by the emissive features of ZnII complexes based on bis-Schiff base ligands, bis-ZnII salphen complexes bearing pyridyl functionalized ligands have been successfully synthesized. Their photophysical features, electrochemical behavior and electroluminescent (EL) properties have been investigated in detail. The functionalized bis-ZnII salphen complexes can exhibit high thermal stability up to 417 °C, and their photoluminescence (PL) spectra show a maximal emission wavelength peak at ca. 565 nm both in solution and PMMA doped films. The PL investigation of the neat films for these functionalized bis-ZnII salphen complexes indicated that the pyridyl functionalized ligands can effectively reduce the degree of molecular aggregation to enhance their emission intensity. Taking advantage of the charge carrier injection/transporting ability of the pyridyl functionalized ligands and their dendritic design, the optimized EL devices fabricated by a simple solution-processing method can achieve a peak luminance (Lmax) of 3589 cd m-2, a maximal external quantum efficiency (ηext) of 1.46%, a maximal current efficiency (ηL) of 4.1 cd A-1 and a maximal power efficiency (ηp) of 3.8 lm W-1. These results should afford important instructions for exploiting high performance fluorescent emitters based on dinuclear ZnII complexes.

High Triplet Energy Level Achieved by Tuning the Arrangement of Building Blocks in Phosphorescent Polymer Backbones for Furnishing High Electroluminescent Performances in Both Blue and White Organic Light-Emitting Devices.

A high triplet energy level (ET) of ca. 2.83 eV has been achieved in a novel polymer backbone through tuning the arrangement of two kinds of building blocks, showing enhanced hole injection/transporting capacity. Based on this new polymer backbone with high ET, both blue and white phosphorescent polymers were successfully developed with a trade-off between high ET and enhanced charge-carrier transporting ability. In addition, their photophysical features, electrochemical behaviors, and electroluminescent (EL) properties have been characterized in detail. Benefitting from the advantages associated with the novel polymer backbone, the blue phosphorescent polymers show top-ranking EL performances with a maximum luminance efficiency (ηL) of 15.22 cd A-1, corresponding to a power efficiency (ηP) of 12.64 lm W-1, and external quantum efficiency (ηext) of 6.22% and the stable Commission Internationale de L'Eclairage (CIE) coordinates of (0.19, 0.38). Furthermore, blue-orange (B-O) complementary-colored white phosphorescent polymers based on this novel polymer backbone were also obtained showing encouraging EL efficiencies of 12.34 cd A-1, 9.59 lm W-1, and 4.10% in the optimized WOLED together with exceptionally stable CIE coordinates of (Δx = 0.014, Δy = 0.010) in a wide driving voltage range from 4 to 16 V. All of these attractive EL results achieved by these novel phosphorescent polymers show the great potential of this new polymer backbone in developing highly efficient phosphorescent polymers.

Pyrimidine-Based Mononuclear and Dinuclear Iridium(III) Complexes for High Performance Organic Light-Emitting Diodes.

Containing two nitrogen atoms, the electron-deficient pyrimidine ring has excellent coordinating capability with transition metal ions. However, compared with the widely used pyridine ring, applications of the pyrimidine ring in phosphorescent Ir(III) complexes are rare. In this research, two highly emissive pyrimidine-based mononuclear Ir(III) complexes and their corresponding dinuclear Ir(III) complexes were prepared with a simple one-pot reaction. The incorporation of the second Ir(III) center can lead to dramatic differences of both photophysical and electrochemical properties between the mono- and dinuclear complexes. Besides, these properties can also be fine-tuned with different substituents. Theoretical calculations have also been performed to understand their photophysical behaviors. The electroluminescent investigations demonstrate that the pyrimidine-based mono- and dinuclear Ir(III) complexes could show impressive device performance. The vacuum-deposited organic light-emitting diode (OLED) based on the mononuclear Ir(III) complex exhibited an external quantum efficiency (EQE) of 16.1% with almost no efficiency roll-off even at 10 000 cd m-2. More encouragingly, the solution-processed OLED based on the dinuclear Ir(III) complex achieved the outstanding EQE, current efficiency (CE), and power efficiency (PE) of 17.9%, 52.5 cd A-1, and 51.2 lm W-1, respectively, representing the highest efficiencies ever achieved by OLEDs based on dinuclear Ir(III) complexes.