Transition Metal‐Free Carbazole Synthesis from Arylureas and Cyclohexanones

An efficient strategy for carbazole synthesis from arylureas and cyclohexanones under transition metal‐free conditions has been developed. The combined use of potassium iodide and iodine could significantly improve the reaction efficiency to provide 2,6‐disubstituted 9‐arylcarbazoles in moderate to good yields. In this kind of transformation, the whole carbazole moiety (except the nitrogen atom) comes from two equivalents of cyclohexanones.

     

Solution‐Processible 2,2′‐Dimethyl‐biphenyl Cored Carbazole Dendrimers as Universal Hosts for Efficient Blue,Green, and Red Phosphorescent OLEDs

A series of solution‐processible 2,2′‐dimethyl‐biphenyl cored dendrimers, namely G1MP, G2MP, and G3MP, is designed and synthesized by tuning the generation of periphery carbazole dendron. The resulting dendrimers all show excellent solubility in common organic solvents, and their high‐quality thin films can be formed via spin‐coating with a root‐mean‐square roughness in the range of 0.38–0.54 nm. G3MP, which contains the third‐generation carbazole dendron, has the greatest potential among those made here as an ideal universal host for multicolored triplet emitters. G3MP exhibits good thermal stability, with a glass transition temperature of 368 °C, a triplet energy as high as 2.85 eV enough to prevent the loss of triplet excitons, and suitable HOMO/LUMO levels of –5.30/–2.11 eV to facilitate both hole and electron injection and transport. When using G3MP as the host, highly efficient deep‐blue, blue, green, and red phosphorescent organic light‐emitting diodes (PhOLEDs) are successfully demonstrated, revealing a maximum luminous efficiency up to 18.2, 28.2, 54.0, and 12.7 cd A^–1 with the corresponding Commission Internationale de L'Eclairage (CIE) coordinates of (0.15, 0.23), (0.15, 0.35), (0.38, 0.59), and (0.64, 0.34), respectively. The state‐of‐art performance indicates that dendritic hosts have a favorable prospect of applications in solution‐processed white PhOLEDs and full‐color displays.     

A Multifunctional Iridium‐Carbazolyl Orange Phosphor for High‐Performance Two‐Element WOLED Exploiting Exciton‐Managed Fluorescence/Phosphorescence

By attaching a bulky, inductively electron‐withdrawing trifluoromethyl (CF₃) group on the pyridyl ring of the rigid 2‐[3‐ (N‐phenylcarbazolyl)]pyridine cyclometalated ligand, we successfully synthesized a new heteroleptic orange‐emitting phosphorescent iridium(III) complex [Ir( L ₁ )₂(acac)] 1 ( HL ₁ = 5‐trifluoromethyl‐2‐[3‐(N‐phenylcarbazolyl)]pyridine, Hacac = acetylacetone) in good yield. The structural and electronic properties of 1 were examined by X‐ray crystallography and time‐dependent DFT calculations. The influence of CF₃ substituents on the optical, electrochemical and electroluminescence (EL) properties of 1 were studied. We note that incorporation of the carbazolyl unit facilitates the hole‐transporting ability of the complex, and more importantly, attachment of CF₃ group provides an access to a highly efficient electrophosphor for the fabrication of orange phosphorescent organic light‐emitting diodes (OLEDs) with outstanding device performance. These orange OLEDs can produce a maximum current efficiency of ～40 cd A^?1, corresponding to an external quantum efficiency of ～12% ph/el (photons per electron) and a power efficiency of ～24 lm W^?1. Remarkably, high‐performance simple two‐element white OLEDs (WOLEDs) with excellent color stability can be fabricated using an orange triplet‐harvesting emitter 1 in conjunction with a blue singlet‐harvesting emitter. By using such a new system where the host singlet is resonant with the blue fluorophore singlet state and the host triplet is resonant with the orange phosphor triplet level, this white light‐emitting structure can achieve peak EL efficiencies of 26.6 cd A^?1 and 13.5 lm W^?1 that are generally superior to other two‐element all‐fluorophore or all‐phosphor OLED counterparts in terms of both color stability and emission efficiency.     

Microenvironment-Sensitive Fluorescent Ligand Binds Ascaris Telomere Antiparallel G-Quadruplex DNA with Blue-Shift and Enhanced Emission

The development of small molecules that can selectively target G-quadruplex (G4) DNAs has drawn considerable attention due to their unique physiological and pathological functions. However, only a few molecules have been found to selectively bind a particular G4 DNA structure. We have developed a fluorescence ligand Q1 , a molecular scaffold with a carbazole–pyridine core bridged by a phenylboronic acid side chain, that acts as a selective ascaris telomere antiparallel G4 DNA ASC20 ligand with about 18 nm blue-shifted and enhanced fluorescence intensity. Photophysical properties revealed that Q1 was sensitive to the microenvironment and gave the best selectivity to ASC20 with an equilibrium binding constant K_a=6.04×10⁵ M⁻¹. Time-resolved fluorescence studies also demonstrated that Q1 showed a longer fluorescence lifetime in the presence of ASC20. The binding characteristics of Q1 with ASC20 were shown in detail in a fluorescent intercalator displacement (FID) assay, a 2-Ap titration experiment and by molecular docking. Ligand Q1 could adopt an appropriate pose at terminal G-quartets of ASC20 through multiple interactions including π–π stacking between aromatic rings; this led to strong fluorescence enhancement. In addition, a co-staining image showed that Q1 is mainly distributed in the cytoplasm. Accordingly, this work provides insights for the development of ligands that selectively targeting a specific G4 DNA structure.     

Synthesis and antiproliferative activity of some ellipticine-like 11H-pyrido[a]carbazole derivatives

Some modified 11H-pyrido[a]carbazoles (11H-PyC) and their corresponding tetrahydro derivatives (11H-THPyC) were prepared. A common multistep pathway characterized by conventional reactions, including a Fischer-indole-type synthesis, yielded the tetracyclic compounds. To improve cytotoxicity, 11H-PyC and 11H-THPyC derivatives were endowed with a diethylaminoethyl side chain. The antiproliferative activity was assessed in three human tumor cell lines, and a number of derivatives showed a cytotoxic effect in agreement with their capacity to form a molecular intercalative complex with DNA and to interfere with the relaxation activity of DNA topoisomerase II. In contrast, three derivatives that exhibited significant antiproliferative efficacy, showed no inhibition of topoisomerase II, thus suggesting an unexpected and novel mode of action for these ellipticine-like compounds independent of topoisomerase II activity.     

N-烷基咔唑的合成研究

咔唑及其衍生物是合成新型光电材料的原料,已经引起人们的重视。我们用相转移催化的方法合成了三种Ｎ－烷基咔唑,所合成的化合物,经过熔点测定,元素分析和红外光谱分析确证了它们的结构。结果表明,溴代烷上烷基给电子能力大小,对合成反应产生规律性的影响     

Bipolar Hosts Based on a Rigid 9,10-Dihydroanthracene Scaffold for Full-Color Electrophosphorescent Devices

Two bipolar hosts, CzDPO and CzDOxa , comprising a hole-transporting carbazole and an electron-transporting diphenyl phosphine oxide or oxadiazole with a saturated linker (9,10-dihydroanthracene) have been synthesized and characterized. The saturated linker limited the effective extension of π conjugation, leading to high triplet energies (E_T=2.97–2.98 eV). The diastereomers with a rigid configuration provided an amorphous thin film with high thermal (T_d=415–444 °C) and morphological stability (T_g=188–224 °C). The high triplet energies and bipolar carrier transport characteristics (ambipolariy) of CzDPO and CzDOxa can facilitate exothermic energy transfer to the dopants and balance carrier injection/transport in the emission layers. As a result, they were utilized as universal hosts for various phosphorescent OLEDs (from blue to red), showing average external quantum efficiencies (η_ext=8.2–13.1 %) and low efficiency roll-off. In addition, we also fabricated dual-emitter white organic light-emitting diodes with a co-doped single emissive layer. WOLED hosted by CzDOxa exhibited satisfactory device efficiencies (14.4 %, 25.7 cd A⁻¹, 27 lm W⁻¹) with highly stable chromaticity (CIE_x=0.26–0.28 and CIE_y=0.38) at brightnesses from 560 to 15200 cd m⁻².