咔唑与N-烷基咔唑光物理行为的差异

已知甲基、乙基咔唑等咔唑的衍生物与对位苯二甲酸二甲酯(DMTP)和邻位苯二甲酸二甲酯(DMP)可以形成激基复合物^[1],但是咔唑与DMTP或DMP相互作用时观察不到激基复合物的荧光。     

Luminescence properties of PPV derivatives bearing substituted carbazole pendants

A series of PPV derivatives bearing substituted and unsubstituted carbazole and 2-ethylhexyloxy pendants were prepared and their photo- (PL) and electroluminescence (EL) properties were studied. Substituted carbazole structures were N-phenylcarbazole and 3,6-dimethoxycarbazole. The substituents on the carbazole pendants caused little change in UV-vis absorption, PL, and EL when compared with the polymer bearing the unsubstituted carbazole pendants. The presence of the benzene ring between the main chain and the carbazole pendant increased the threshold electric field in EL. We could obtain maximum brightness of ca. 17,000 - 30,000 cd/m² for the polymers carrying the unsubstituted and dimethoxy substituted carbazole pendants.     

Solubility of carbazole in binary chloroalkane + dibutyl ether solvent mixtures

Solubilities are reported for carbazole in three binary chloroalkane + dibutyl ether solvent mixtures at 25°C. Results of these measurements are compared with solution models developed for solubility in systems containing specific solute-solvent interactions. A simple model based on a single 1:1 carbazole:dibutyl ether complex described the solubility data, though the calculated equilibrium constant was about one-half of values published previously. A more sophisticated solution model, which assumes both carbazole:dibutyl ether and carbazole:chloroalkane complexes, was needed to thermodynamically describe the systems studied. Equilibrium constants for three presumed carbazole:chloroalkane complexes are calculated from measured carbazole solubilities.     

咔唑双乙酰化衍生物的合成及其电子光谱

以咔唑为原料,通过SN1亲核取代和Friedel-Crafts亲电取代反应合成了咔唑双乙酰化衍生物——3,6-二乙酰基-N-乙基咔唑和3,6-二乙酰基-N-丁基咔唑,其结构经1H NMR,IR,MS和元素分析表征,并讨论了它们的电子吸收光谱。     

Hydrogen atom transfer reaction from excited carbazole to pyridine

The hydrogen bonding interaction between excited carbazole and pyridine was investigated in cyclohexane by an emission—absorption flash technique. Triplet carbazole is deactivated by pyridine with a rate constant of 4.9 × 10⁷ M⁻¹ s⁻¹, yielding the carbazyl radical with a reaction yield of unity. The triplettriplet absorption of carbazole hydrogen bonded with pyridine was not observed. By means of the triplet energy transfer from N-ethylcarbazole to the hydrogen-bonded carbazole it was found that the triplet state of the hydrogen-bonded carbazole yields the carbazyl radical wtih a reaction yield of 0.7. Excited singlet carbazole is deactivated by pyridine with a diffusion-controlled rate, yielding the carbazyl radical with a reaction yield of 0.1. Flashing of the hydrogen-bonded carbazole does not yield carbazyl radical. The difference in the reaction yields between the free and the hydrogen-bonded species indicates that the dynamic hydrogen atom transfer reaction occurs from the encounter state in competition with hydrogen bond formation.     

Carbazole compounds as host materials for triplet emitters in organic light-emitting diodes: tuning the HOMO level without influencing the triplet energy in small molecules

A series of novel carbazole compounds was synthesized and tested for their suitability as host for triplet emitters in an organic-light emitting diode (OLED). In these compounds, a carbazole unit is either connected to other carbazole units to form carbazole dimers and trimers or to fluorene and oxadiazole derivatives to form mixed compounds. The HOMO level of carbazole compounds can be tuned by substitution at the 3, 6, and/or 9 positions. Making oligomers by connecting carbazole molecules via their 3 (3') positions shifts the HOMO level to higher energy, while replacing alkyl groups at the 9 (9') positions by aryl groups shifts the HOMO level to lower energy. Furthermore, it has been found that the triplet energy of these compounds is determined by the presence of poly(p-phenyl) chains in the molecular structure. By identifying the longest poly(p-phenyl) chain, one can predict whether a compound will be a suitable host for a high-energy triplet emitter. An overview of HOMO levels, singlet and triplet levels, and exchange energies is given for all carbazole compounds synthesized. Finally, OLEDs employing two selected carbazole compounds as host and fac-tris(2-phenylpyridine)-iridium (Ir(ppy)(3)) as guest were constructed and characterized electrically.     

Photosensitization of carbazole derivatives in cationic polymerization with a novel sensitivity to near‐UV light

Photosensitizers based on the carbazole structure were designed and developed for cationic polymerization. Along with triarylsulfonium and diaryliodonium salts, the carbazole derivatives showed a high photosensitization effect in the cationic photopolymerization of epoxides. The photophysical properties of the carbazole derivatives were studied in terms of electronic absorption, fluorescence, and phosphorescence spectrometry. Moreover, a unique photosensitization mechanism of the carbazole derivatives was discussed after studies of the fluorescence quenching, redox behavior, and kinetics of the photopolymerization by time‐resolved fluorescence spectrometry, cyclic voltammetry, and photo differential scanning calorimetry, respectively. The results confirmed the redox photosensitization of the carbazole derivatives in cationic polymerization. The photosensitization of the carbazole and its ring or N‐alkylated derivatives occurred predominantly in singlet excited states at the rate of the diffusion limit, whereas the carbazole derivatives with carbonyl substituents sensitized onium salts via triplet excited states on the basis of the Rehm–Weller equation in the photoinduced electron‐transfer process. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 90–100, 2000     

Effet de la substitution par un groupement phényle sur les spectres électroniques du carbazole

The electronic absorption and fluorescence spectra of carbazole and 9-phenylcarbazole have been studied in different solvents. Comparison of the spectroscopic data shows that the effect of the interaction of phenyl-substituted carbazole with the solvent is the same as that of the carbazole completed by hydrogen bonding.     

"一锅法"合成N-乙基咔唑乙酰化衍生物

以N-乙基咔唑为原料,通过“一锅法”合成了未见文献报道的单乙酰化衍生物3-乙酰基-9-乙基咔唑和双乙酰化衍生物3,6-二乙酰基-9-乙基咔唑,其结构经1H NMR,IR,MS和元素分析表征。     

烷基步长对聚丙烯酸修饰咔唑电聚合的影响

合成了含有不同烷基链取代的N-丙烯酰氧癸基咔唑(MACZ10)和N-丙烯酰氧十二烷基咔唑(MACZ12), 通过自由基聚合得到聚N-丙烯酰氧烷基咔唑(PMACZ). 分子量分析表明, 随着烷基链长度的增加, 聚合物分子量减小, 分布变宽. 荧光光谱表明, 随着烷基链长度的增加, 聚合物在353 nm处的发射峰逐渐减弱. 在四氢呋喃和体积分数为10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中, 直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧烷基咔唑)(PPMACZ)薄膜. PPMACZ薄膜具有良好的氧化还原活性、热稳定性和蓝色发光性能, 聚合物氧化还原可逆性随着烷基链长的增加而增加, 且发射峰变宽.     

A New Poly(fluorene‐co‐carbazole) with a Large Substituent Group at the 9‐Position of the Carbazole Moiety: An Efficient Blue Emitter

Summary: A new poly(fluorene‐co‐carbazole) (PFC‐1) with a large substituent group (ADN, a naphthalene‐anthracene derivative moiety) at the 9‐position of carbazole was synthesized. Compared with poly(fluorene‐co‐carbazole)s that have an alkyl substituent group at the 9‐position of the carbazole, the UV‐vis absorption (or photoluminescent emission) peaks of PFC‐1 are in almost the same position both in solution and in the solid state, whereas films of the former give peaks at longer wavelengths than those in solution. The photoluminescent (PL) spectra of PFC‐1 indicate that the attachment of ADN to the poly(fluorene‐co‐carbazole)s gives rise to an efficient blue emission from non‐aggregated ADN. There is no difference evident between PFC‐1 and other reported poly(fluorene‐co‐carbazole)s in PL quantum yield, thermostability, and electrochemical behavior, which suggests that PFC‐1 is an efficient blue emitter.

UV‐Vis spectra of the poly(fluorene‐co‐carbazole) (PFC‐1), with a large substituent group (ADN, a naphthalene‐anthracene derivative moiety) at the 9‐position of carbazole, in toluene and in the film.     

Carbazole derivative synthesis and their electropolymerization

This review article investigates the hot topics by presenting the latest advances in carbazole and its derivative synthesis and their electropolymerization processes. The carbazole-based compounds are particularly attractive due to their important photochemical and thermal stability and good hole-transport ability. Conjugated monomers of carbazole derivatives and their polymers attract interest due to their suitability in a broad range of applications, such as biosensors, corrosion inhibition, photovoltaics, electroluminescent devices, field-effect transistors and supercapacitors, etc. This review article divides two main parts. One of them includes effects of electropolymerization parameters of carbazole and chemical polymerization of carbazole derivatives. In addition, copolymers and composites of carbazole derivatives were presented in the first part. In the second part, the application of polycarbazole and its derivatives was examined as biosensors, corrosion inhibition, supercapacitor, battery, fuel cell, solar cell, electropolymerization, light emitting diodes, and OLEDs.     

痂囊腔菌素A与咔唑化合物间的光致电子转移

研究了咔唑、咔唑-9-乙酸、3-溴-咔唑-9-乙酸在缺氧条件下对天然苝醌化合物痂囊腔菌素A(简记为EA)的荧光猝灭行为;由竹红菌甲素(HA)和乙素(HB)的荧光寿命估算了EA在乙腈中的荧光寿命,并进而计算了三个咔唑化合物的双分子猝灭速度常数.结果表明,三个咔唑化合物在EA的可见光吸收区无光吸收,据此推测其对EA的荧光猝灭作用归因于咔唑化合物作为电子给体而EA作为电子受体的光致电子转移作用.三个咔唑化合物的Stern-Volmer猝灭常数分别为698、704和1 063L·mol-1;乙酸基对咔唑环的光致电子转移速率几乎没有影响,而溴原子取代能够增加咔唑化合物对EA的荧光猝灭程度和光致电子转移速率.此外,EA在乙腈中的荧光寿命为1.98ns,而三个咔唑化合物的双分子猝灭速率常数分别为3.52×1011,3.56×1011和5.37×1011 L·mol-1·s-1.     

New Synthesis Method of N-Alkylation of Carbazole Under Microwave Irradiation in Dry Media.

Under microwave irradiation carbazole reacts remarkably fast with a number of alkyl halides to give N-alkyl derivatives of carbazole. The reaction were carried out with high yield by simply mixing carbazole with an alkyl halide which was adsorb on potassium carbonate.     

Discovery of Novel D‐A and D‐π‐A Structured Carbazole‐Based Formazan Dyes: Synthesis,Characterization, and Spectroscopic Studies

In the current study, new carbazole‐based formazan dyes, D‐A and D‐π‐A, were synthesized, and their spectroscopic properties were studied for the first time. For this aim, carbazole aldehyde compounds were modified by the derivatization of carbazole, a natural electron‐donor compound, from 3‐ and 9‐position. Then, hydrazone derivatives were synthesized from these aldehyde derivatives. Finally, D‐A ( 5A–C ) and D‐π‐A ( 6A–C ) carbazole–formazan dyes were obtained by the interaction of the hydrazone compounds with p‐substituted aniline. After characterization of the structures of these compounds, photophysical properties of the carbazole–formazans were studied in the different polarity media (i.e., acetonitrile, toluene, and chloroform) in order to detect the solvent effects. Because of the π‐conjugated bridge and the electron acceptor nitro group at the para position, D‐π‐A structured carbazole–formazan dye 6C showed the highest Stokes shift of 155 nm.     

A computational study of substituent effects on the stability and geometry of carbazole‐pyridine complexes

Hydrogen bonding between carbazole and pyridine is known to quench fluorescence emission of carbazole. Three carbazolopyridinophanes—compounds composed of carbazole and pyridine subunits such that an intramolecular hydrogen bond may exist between them—have been pursued as reversible fluorescent sensors that detect given analytes through fluorescence restoration. However, these sensors exhibit background fluorescence believed to be related to the proportion of non‐hydrogen‐bonded conformers present. In this computational investigation, the potential energy surfaces of various hydrogen‐bonded carbazole:pyridine complexes are investigated using density functional theory with the intent of explaining the observed background fluorescence for the carbazolopyridinophanes. The results indicate carbazolopyridinophane conformers most resembling the geometry of their corresponding free carbazole:pyridine complexes exhibit the least background fluorescence.     

Incorporation of an indole-containing diarylbutylamine pharmacophore into furo[2,3-a]carbazole ring systems

Due to concurrent oxidation of the indole moiety in the starting carbazole alkenol, an epoxidation route aiming at incorporation of a conformationally constrained diarylbutylamine failed to give the desired furo[2,3-a]carbazole ring system. Instead, an indole epoxide intermediate was generated, which underwent rearrangement involving participation of a vicinal OH group. The required furo[2,3-a]carbazole could, however, be accessed via a Hg²⁺-induced cyclisation of a carbazole alkynol.     

Etude du complexe par liaison hydrogène du carbazole à l'état fondamental par spectroscopie UV

The modifications of UV absorption spectra of carbazole show the hydrogen bonding complex in the ground state. The red shifts of carbazole absorption spectra in solvents able to form a complex are more important than those obtained in aprotic solvents, with high polarity. The solvents with OH groupment can interact with carbazole to form NH ⋯ O and OH ⋯ π type hydrogen bonds.     

Synthesis and characterization of three organic dyes with various donors and rhodanine ring acceptor for use in dye-sensitized solar cells

A series of new organic dyes comprising carbazole, iminodibenzyl, and phenothiazine moieties as the electron donors and rhodanine ring as the electron acceptor/anchoring groups were designed and developed for use in dye-sensitized solar cells. HOMO and LUMO energy level tuning was achieved by varying the carbazole, iminodibenzyls and phenothiazine donors. This was evidenced by spectral and electrochemical experiments and density functional theory calculations. Electrochemical studies indicated that the phenothiazine unit was much more effective in lowering the ionization potential than were the iminodibenzyl and carbazole units. The phenothiazine dye shows a solar-energy-to-electricity conversion efficiency (η) of 4.87%; the carbazole and iminodibenzyl dyes show η of 2.54% and 3.52%, respectively. These findings reveal that using carbazole, iminodibenzyl and phenothiazine donors as light-harvesting sensitizers are promising candidates for dye-sensitized solar cells.     

Electronic structures of carbazole and its derivatives: A semi-empirical study on the substitution effects of carbazole

The electronic structures of carbazole, N-phenylcarbazole (NPC), cyanophenylcarbazole (CPC) and N-ethylcarbazole (NEC) have been calculated using the quantum chemical semi-empirical MINDO/3 method. In this paper, electronic ground states and first singlet excited states of the systems mentioned were investigated. It is observed that the excitation energy of carbazole based on the calculated difference in heats of formation agrees quite well with experimental data obtained from supersonic expansion studies. Calculated energy levels of molecular orbitals and their graphical forms are used qualitatively in elucidating the S₀ → S₁ excitation electronic origin red shifts observed in carbazole derivatives with respect to the electronic origin of the parent carbazole. It is noted that the red shifts are not just a result of the destabilization of the HOMO of carbazole but are also determined by the nature of the substituting moieties. It is also observed that the LUMO of CPC is not derived from the parent carbazole which partially explains the difference in electronic behaviour as compared with the other derivatives.