Tetradentate Pt(II) Complexes with Bulky Carbazole Moieties for High-Efficiency and Narrow-Emitting Blue Organic Light-Emitting Devices.

Blue tetradentate Pt(II) complexes, Pt-tBuCz and Pt-dipCz, are synthesized by introducing carbazoles with bulky substituents for improving the rigidity and inhibiting intermolecular interactions of phosphorescent emitter. tert-Butyl and 2,6-diisopropylphenyl groups are substituted as the blocking groups at 3 position of the carbazole in Pt-tBuCz and Pt-dipCz, respectively. These new phosphorescent emitters exhibit a narrow full width at half maximum (FWHM) and a high horizontal emitting dipole orientation ratio. Pt-dipCz demonstrates a small FWHM of 24 nm, a high emitting dipole orientation ratio of 81%, and a high photoluminescence quantum yield value of 94%. As a result, the Pt-tBuCz and Pt-dipCz devices exhibited external quantum efficiencies (EQEs) of 23.7% and 25.0% with small FWHMs of 25 and 22 nm, respectively. For the Pt-dipCz device, the small FWHM and high EQE of >20% are maintained even at a doping concentration of 20 wt%. Furthermore, phosphor-sensitized organic light-emitting diodes fabricated using Pt-dipCz as a sensitizer achieved a high EQE of 31.4% with an FWHM of 18 nm. This result indicates that the 2,6-diisopropylphenyl group is a effective blocking group for Pt(II) complexes to develop highly efficient, color stable, doping concentration resistant, and efficiently sensitizing blue phosphors.

Fused Cycloalkyl Unit-Functionalized Tetradentate Pt(II) Complexes for Efficient and Narrow-Emitting Deep Blue Organic Light-Emitting Diodes.

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.

Solution-Processed Pure Red TADF Organic Light-Emitting Diodes With High External Quantum Efficiency and Saturated Red Emission Color.

In spite of recent research progress in red thermally activated delayed fluorescence (TADF) emitters, highly efficient solution-processable pure red TADF emitters are rarely reported. Most of the red TADF emitters reported to date are designed using a rigid acceptor unit which renders them insoluble and unsuitable for solution-processed organic light-emitting diodes (OLEDs). To resolve this issue, a novel TADF emitter, 6,7-bis(4-(bis(4-(tert-butyl)phenyl)amino)phenyl)-2,3-bis(4-(tert-butyl)phenyl)quinoxaline-5,8-dicarbonitrile (tBuTPA-CNQx) is designed and synthesized. The highly twisted donor-acceptor architecture and appropriate highest occupied molecular orbital/lowest unoccupied molecular orbital distribution lead to a very small singlet-triplet energy gap of 0.07 eV, high photoluminescence quantum yield of 92%, and short delayed fluorescence lifetime of 52.4 µs. The peripheral t-butyl phenyl decorated quinoxaline acceptor unit and t-butyl protected triphenylamine donor unit are proven to be useful building blocks to improve solubility and minimize the intermolecular interaction. The solution-processed OLED based on tBuTPA-CNQx achieves a high external quantum efficiency (EQE) of 16.7% with a pure red emission peak at 662 nm, which is one of the highest EQE values reported till date in the solution-processed pure red TADF OLEDs. Additionally, vacuum-processable OLED based on tBuTPA-CNQx exhibits a high EQE of 22.2% and negligible efficiency roll-off.

Selective B(5,8,9)-Triarylation Reaction of o-Carboranes through Determination of the Order of Introduction of Aryl Groups into B(4)-Acylamino-o-carboranes.

Palladium-catalyzed iterative cage B-H arylation reaction of a wide range of B(4)-acylamino-o-carboranes with aryl iodides has been developed, leading to the formation of B(5,8,9)-triarylated B(4)-acylamino-o-carboranes with excellent regioselectivity. Moreover, B(5,8,9)-triarylated carboranes bearing three different aryl groups were synthesized from B(4)-acylamino-o-carborane and three different aryl iodides. The order of introduction [B(9) > B(8) > B(5)] of aryl groups into the B(5,8,9)-triarylation reaction was determined for the first time through NMR monitoring and X-ray analyses.

Iridium-Catalyzed Cyclative Indenylation and Dienylation through Sequential B(4)-C Bond Formation, Cyclization, and Elimination from o-Carboranes and Propargyl Alcohols.

Described herein is the first iridium-catalyzed cyclative indenylation through sequential B(4)-C and intramolecular C-C bond formation from o-carboranes and propargyl alcohols, leading to the formation of B(4)-indenylated o-carboranes with excellent regioselectivity via direct B-H activation. Moreover, the iridium-catalyzed regioselective 1,3-dienylation has been accessed through sequential B-H activation, dehydration, and decarboxylation, producing B(4)-dienylated o-carboranes.