ABSTRACT
The tetradentate ligand, merging a carbazole unit with high triplet energy and dimethoxy bipyridine, renowned for its exceptional quantum efficiency in coordination with metals like Pt, is expected to demonstrate remarkable luminescent properties. However, instances of tetradentate ligands such as bipyridine-based pyridylcarbazole derivatives remain exceptionally scarce in the current literature. In this study, we developed a tetradentate ligand based on carbazole and 2,3'-bipyridine and successfully complexed it with Pt(II) ions. This novel compound (1) serves as a sky-blue phosphorescent material for use in light-emitting diodes. Based on single-crystal X-ray analysis, compound 1 has a distorted square-planar geometry with a 5/6/6 backbone around the Pt(II) core. Bright sky-blue emissions were observed at 488 and 516 nm with photoluminescent quantum yields of 34% and a luminescent lifetime of 2.6 µs. TD-DFT calculations for 1 revealed that the electronic transition was mostly attributed to the ligand-centered (LC) charge transfer transition with a small contribution from the metal-to-ligand charge transfer transition (MLCT, ~14%). A phosphorescent organic light-emitting device was successfully fabricated using this material as a dopant, along with 3'-di(9H-carbazol-9-yl)-1,1'-biphenyl (mCBP) and 9-(3'-carbazol-9-yl-5-cyano-biphenyl-3-yl)-9H-carbazole-3-carbonitrile (CNmCBPCN) as mixed hosts. A maximum quantum efficiency of 5.2% and a current efficiency of 15.5 cd/A were obtained at a doping level of 5%.
ABSTRACT
Two-coordinate coinage metal complexes have emerged as promising emitters for highly efficient organic light-emitting devices (OLEDs). However, achieving efficient long-wavelength electroluminescence emission from these complexes remains as a daunting challenge. To address this challenge, molecular design strategies aimed at bolstering the photoluminescence quantum yield (Φ) of Au(I) complex emitters in low-energy emission regions are investigated. By varying amido ligands, a series of two-coordinate Au(I) complexes is developed that exhibit photoluminescence peak wavelengths over a broad range of 533-750 nm. These complexes, in particular, maintain Φ values up to 10% even in the near-infrared emission region, overcoming the constraints imposed by an energy gap. Quantum chemical calculations and photophysical analyses reveal the action of radiative control, which serves to overcome the energy gap law, becomes more pronounced as the overlap between hole and electron distributions (Sr (r)) in the excited state increases. It is further elucidated that Sr (r) increases with the distance between the hole-distribution centroid and the nitrogen atom in an amido ligand. Finally, multilayer OLEDs involving the Au(I) complex emitters exhibit performances beyond the borderline of the electroluminescence wavelength-external quantum efficiency space set by previous devices of coinage metal complexes.
ABSTRACT
A blue tetradentate Pt(II) complex named Pt-tmCyCz is developed by introducing a cycloalkyl unit fused to carbazole to improve the rigidity and bulkiness of the complex. The introduction of the tetramethylcyclohexyl (tmCy) group results in a narrow full width at half maximum (FWHM), a high horizontal emitting dipole orientation, doping concentration resistant stable spectrum, and extremely small efficiency roll-off, and little concentration quenching effect. Phosphorescent organic light-emitting diodes (OLEDs) doped with Pt-tmCyCz achieve a high external quantum efficiency (EQE) of 21.5%, with a small EQE roll-off of 3.8% up to 1000 cd m-2 , a small FWHM of 24 nm, and a color coordinate of (0.132, 0.138). Moreover, Pt-tmCyCz is investigated as a sensitizer in phosphor-sensitized OLEDs using N7 ,N7 ,N13 ,N13 ,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine (νDABNA) as a terminal emitter. The Pt-tmCyCz:νDABNA device achieves a high EQE of 33.9%, with a small EQE roll-off of only 8.0% up to 1 000 cd m-2 . The results demonstrate that fused tmCy group in carbazole can be an effective building block for the development of high-performance Pt(II) complexes, which can be utilized as efficient phosphors or sensitizers in OLEDs.
ABSTRACT
Device degradation in red hyperfluorescent organic light-emitting diodes is primarily caused by exciton energy loss due to Dexter energy transfer (DET) from a thermally activated delayed fluorescence (TADF) assistant dopant to a fluorescent dopant. In this work, the donor segments in the TADF assistant dopants were delicately modulated to suppress DET for high efficiency. The derived benzothienocarbazole donors were introduced to the TADF assistant dopants instead of carbazole, and they accelerated the reverse intersystem crossing of the TADF assistant dopant and managed the DET from the TADF assistant dopant to the fluorescent dopant. As a result, the red TADF-assisted device showed a high external quantum efficiency of 14.7% and improved the device lifetime by 70% compared to a well-known TADF-assisted device.
