N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二氨基苯基)咔唑的合成

以2,7-二溴咔唑为原料经过N-烷基化、Suzuki偶联反应、Buchwald-Hartwig偶联反应合成了N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二氨基苯基)咔唑。利用NMR、IR和熔点等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了化合物的热稳定性和光学性能。该化合物可用作有机发光二极管(OLED)的空穴传输材料。     

N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺的合成

以3,5-二溴苯胺,碘苯和咔唑为原料,经取代和Ullmann反应合成了一个新的含咔唑三苯胺化合物——N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺,其结构经1H NMR,13C NMR和ESI-MS表征。     

含二苯胺2,6-二咔唑基吡啶共轭化合物的合成

以咔唑,2,6-二溴吡啶和二苯胺为原料,经Ullmann和碘代反应合成了4个含二苯胺2,6-二咔唑基吡啶共轭化合物:3-二苯胺基-2,6二咔唑基吡啶,3,3’-二(二苯胺基)-2,6-二咔唑基吡啶,3,3’,6-三(二苯胺基)-2,6-二咔唑基吡啶和3,3’,6,6’-四(二苯胺基)-2,6-二咔唑基吡啶,其结构经1H NMR和IR确证。     

七元瓜环与N,N’-二烷基-1,3-(4,4’-二吡啶基)丙烷衍生物的相互作用

以1,3-(4,4’-二吡啶基)丙烷为母体, 合成了N,N’-二乙基、二丁基、二己基以及二辛基1,3-(4,4’-二吡啶基)丙烷衍生物. 利用1H NMR技术和紫外吸收光谱法, 考察了Q[7]与上述链状吡啶衍生物的相互作用. 实验结果表明, Q[7]与客体PC0, PC2作用, 瓜环包结客体的二吡啶基丙烷部分形成1∶1的包结配合物; 对于取代烷基碳链数大于4的N,N’-二烷基-1,3-(4,4’-二吡啶基)丙烷衍生物, 随着主体与客体摩尔比值的增加, 体系中主-客体相互作用的主导模式是Q[7]逐渐包结了客体二吡啶基丙烷部分, 进而形成Q[7]包结客体两端取代烷基, 甚至形成一个客体分子上“挂满”3个主体瓜环的包结物.     

2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶的合成及其光谱性能

以咔唑和2,5-二溴吡啶为初始原料,经Ullmann反应、NBS亲电取代反应和Suzuki偶联等反应,合成了一种新型的磷光配体2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶(5),其结构经1HNMR,ESI-MS及元素分析表征。研究了5在二氯甲烷中的荧光光谱和紫外吸收光谱。     

新型二胺类空穴传输材料的合成与性能研究

以咔唑为初始原料,经NBS亲电取代、Ullmann和Buchwald-Hartwig偶联等反应,合成了有机发光二极管(OLED)空穴传输材料N4,N4’-二(9,9-二甲基芴-2-基)-N4,N4’-二(9-苯基咔唑-3-基)-(1,1’-联苯基)-4,4’-二胺,利用1H NMR、13C NMR、IR和MS等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了物质的热稳定性和光学性能。     

1,4-二[(9-苯基)-9H-3-咔唑基)]苯的合成及其光电性能

以对二溴苯和(9-苯基)-9H-3-咔唑硼酸为原料,通过Suzuki偶联反应合成了一种新型含咔唑磷光主体材料——1,4-二[(9-苯基)-9H-3-咔唑基)]苯(1),其结构经1H NMR,13C NMR和IR表征。UV,荧光光谱和循环伏安法的光电性能研究结果表明,1具有咔唑基团的紫外-可见吸收和荧光特性,与4,4-二(9-咔唑)联苯相比,最低空轨道的能级降低。     

1-(4-吡啶基)苯基-3,5-二[4-(9’H-9’-咔唑基)苯基]苯的合成及其光学性能

以咔唑、对二溴苯、4-溴苯胺和1,3,5-三溴苯为原料,经重氮化、Ullmann反应、硼酸化和Suzuki等反应合成了一种新型的荧光配体———1-(4-吡啶基)苯基-3,5-二[4-(9’H-9’-咔唑基)苯基]苯(6),其结构经1H NMR,MS和元素分析表征。研究了6在二氯甲烷中的紫外吸收光谱和荧光光谱。结果表明,6在237 nm,293 nm和345 nm处有较强吸收;6的最大发射波长在413 nm。     

N,N,N-4,4”-二(4-甲基苯基)-2,2’:6’,2”- 三联吡啶-N,N,N –三异硫氰钌配合物的合成及其在汞离子比色传感中的应用

以2-溴吡啶为原料通过卤素跳舞、Kharash和Stille 偶联反应获得了4,4”-二-(4-甲基苯基)-2,2’:6’,2”-三联吡啶（DPTP），将其作为配体合成了相应的N,N,N-4,4”-二­-(4-甲基苯基)-2,2’:6’,2”-三联吡啶-N,N,N –三异硫氰钌配合物（Ru-DPTP），并通过IR、UV-Vis、ESI-MS和元素分析表征。随着汞离子的加入，Ru-DPTP溶液的最大MLCT态吸收峰由570 nm蓝移到了500 nm，而其它离子对其光谱没有影响，这表明Ru-DPTP可作为汞离子的选择性比色传感器。     

N,N’-双(2’-羟基苯乙酮)缩二胺合锰(Ⅲ)的合成和催化烯烃环氧化研究

本文合成了N,N’-双(2’-羟基苯乙酮)缩乙二胺、N,N’-双(2’-羟基苯乙酮)缩1,2-丙二胺、N,N’-双(2’-羟基苯乙酮)缩1,3-丙二胺和N,N’-双(2’-羟基苯乙酮)缩邻苯二胺四种Schiff配体以及它们的锰(Ⅲ)配合物1,2,3和4。并考察了这四种锰(Ⅲ)配合物作为催化剂,催化以NaOCl为氧源环氧化苯乙烯和环己烯的反应的性能。同时考察了反应温度、助配体、NaOCl的浓度以及pH值对催化环氧化反应的影响。     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

Synthesis of novel twisted carbazole-quinoxaline derivatives with 1,3,5-benzene core: bipolar molecules as hosts for phosphorescent OLEDs

A series of carbazole/quinoxaline hybrids have been synthesized by classic Ullmann and Pd/Cu-catalyzed Sonogashira coupling reaction. Their photophysical, thermal, and electrochemical properties were investigated. The introduction of electron rich carbazole and electron deficient quinoxaline on to the 1,3,5-benzene center leads to a twisted structure with good glass forming property and imparts a bipolar character. The triplet energies in the range of 2.34-2.53 eV indicate them as potential host materials in phosphorescent OLEDs.     

Polycarbazoles via C?N coupling reactions of phthaloyl bis‐9H‐carbazoles with activated difluorides

1,3‐Phthaloyl bis‐9H‐carbazole (MPC) and 1,4‐phthaloyl bis‐9H‐carbazole (PPC) were synthesized by a Friedel‐Crafts reaction of carbazole with terephthaloyl chloride or isophthaloyl chloride. Homopolymers were obtained by a C? N coupling reaction with activated difluorides and copolymers were synthesized with 4,4′‐biphenol as a comonomer by a nucleophilic substitution reaction between these NH‐ and OH‐containing monomers and the activated difluoro monomers. The inherent viscosities of the polymers ranged from 0.35 to 1.03 dL/g. These polymers exhibited glass‐transition temperatures greater than 238 °C with the PPC‐containing homopolymer showing the highest value, 326.4 °C. The thermal stabilities indicated no significant weight loss below 450 °C and the temperatures of 5% weight loss ranged from 514.0 to 546.3 °C. The polymers showed reasonable solubility in organic solvents such as DMAC, DMSO, and NMP. UV absorption and fluorescence emission properties are presented. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4326–4331, 2009     

Synthesis of Spirobifluorene‐alt‐Carbazole Copolymers with Oxadiazole Pendants and their Thermal,Electrochemical, and Photoluminescent Properties

Two new carbazole derivatives with the oxadiazole moiety substituted at the 9 position of carbazole have been facilely synthesized by an aromatic nucleophilic substitution reaction of arylamine and fluoroarenes. Alternating copolymers with spirobifluorene were then prepared by a Suzuki coupling reaction. Spirobifluorene units together with the bulky oxadiazole pendant significantly enhance the morphological stability of the copolymers. An increased π‐electron delocalization in P2 with 2,7‐coupling of carbazole results in a decrease of absorption and phosphorescence emission energies as compared to P1 with 3,6‐coupling of the carbazole. The bandgaps and energy levels of the polymers can be tuned by different coupling positions between carbazole and the spirobifluorene moieties.

     

N-(2-溴乙基)咔唑与N-乙烯基咔唑的气相HeI紫外光电子能谱与电子结构研究

首次报道了N-(2-澳乙基)咔唑和N-乙烯基咏唑的气相Hel紫外光电子能谱(UPS),借助于Gaussian 94采用RHF/6-3lG基组优化几何构型,并用RHF/6-31G基组计算分子轨道及能级.在对咔唑和N-烷基咔唑系列分子UPS电离能变化规律研究的基础上,对这2个分子的UPS谱带给予指认,并讨论其电子结构.结果表明N-(2-溴乙基)咔唑的UPS谱与N-烷基咔唑的不同之处是在10.295,10.540Ve处出现2个Br原子的孤对轨道;N-乙烯基咔唑的UPS谱带与咔唑的相比,电离能变化的特殊性说明乙烯基与咔唑环共平面.     

Synthesis and properties of methoxyphenyl-substituted derivatives of indolo[3,2-b]carbazole

The synthesis and full characterization of new derivatives of indolo[3,2-b]carbazole with differently substituted phenyl groups at nitrogen atoms is reported. Comparative study on their thermal, optical electrochemical, and photoelectrical properties is presented. The synthesized compounds are electrochemically stable. Their highest occupied molecular orbital energy values range from -5.14 to -5.07 eV. The electron photoemission spectra of the films of synthesized materials revealed the ionization potentials of 5.31-5.47 eV. Hole drift mobility of the amorphous film of 5,11-bis(3-methoxyphenyl)-6-pentyl-5,11-dihydroindolo[3,2-b]carbazole exceed 10(-3) cm(2)/V·s at high electric fields, as it was established by xerographic time-of-flight technique. In contrast to diphenylamino substituted derivatives of carbazole, no effect of the position of methoxy groups on the photoelectrical properties was observed for the synthesized methoxyphenyl-substituted derivatives of indolo[3,2-b]carbazole. The indolo[3,2-b]carbazole core has a larger resonance structure that includes 3 phenyl rings, and thus the energy gap of the HOMO and LUMO π orbitals is lower as compared to that of carbazoles. With a larger energy difference between the phenyl substituents and the core moiety, the indolo[3,2-b]carbazole derivatives studied all have a weaker coupling between the phenyl group and a much weaker dependence of the molecular properties on the position of substituents on the phenyl groups as compared to those observed in substituted carbazoles.     

Polycarbazoles: 25 Years of Progress

Summary: Carbazole‐based oligomeric and polymeric materials have been studied for almost 25 years for their unique electrical, electrochemical and optical properties. Interestingly, carbazole units can be linked in two different ways leading to either poly( 3,6 ‐carbazole) or poly( 2,7 ‐carbazole) derivatives. While the former class seems to be very interesting for electrochemical and phosphorescence applications, the latter shows very promising optical properties in the visible range for light emitting diodes (LED). The major intrinsic difference between these two classes is the effective conjugation length: poly(2,7‐carbazole) materials having the longer one, due to their poly(p‐phenylene)‐like structure. Using different synthetic strategies and substitution patterns, the physico‐chemical properties of both classes can be fine‐tuned, leading to high performance materials for a large number electronic applications.

Chemical structures for poly(3,6‐carbazole) and poly(2,7‐carbazole) and the materials used as the starting points for their respective syntheses.     

A New Class of Blue‐Emitting Materials for LED Applications: Triarylamine N‐Functionalised 2,7‐Linked Carbazole Polymers

Attachment of triarylamino‐functional groups at the 9‐position of 2,7‐linked carbazole polymers results in blue‐emitting materials with two independent redox processes that were attributed to the triarylamino groups and the polymer backbone, respectively. This new class of blue‐emitting conjugated polymers was prepared via a Suzuki cross‐coupling reaction and showed low turn‐on voltages in electroluminescent devices as a result of their low ionisation potentials. The photophysical, electrochemical and electroluminescent properties of these materials are discussed.

     

Synthesis, characterization, and properties of 7,7′-bis(3,6-di-tert-butylcarbazol-N-yl)-substituted fluorenyl-oligothiophenes

A series of new 7,7′bis(3,6-di-tert-butylcarbazol-N-yl)-substituted fluorenyl-oligothiophenes bearing 0-, 2-, 4-, 6-, and 8-thiophene rings, namely BCFTn, were synthesized using palladium catalyzed Stille dimerization coupling reactions of their corresponding brominated thiophenes. The relationship between the chemical structure and the properties of these oligomers was evaluated. With respect to the electronic properties, the longest wavelength absorptions, emissions, and also the oxidation potentials can be tuned by varying the conjugation length of the oligothiophene segments. The terminal carbazole and fluorene moieties of the resulting materials are beneficial for their morphology, conjugation length, and solubility.     

1-D and 2-D homoleptic dicyanamide structures, [Ph4P]2[CoII[N(CN)2]4] and [Ph4P][M[N(CN)2]3] (M = Mn, Co)

The homoleptic complexes [Ph(4)P](2)[Co[N(CN)(2)](4)] and [Ph(4)P][M[N(CN)(2)](3)] [M = Co, Mn] have been structurally as well as magnetically characterized. The complexes containing [M[N(CN)(2)](4)](2-) form 1-D chains, which are bridged via a common dicyanamide ligand in [M[N(CN)(2)](3)](-) to form a 2-D structure. The five-atom [NCNCN](-) bridging ligands lead to weak magnetic coupling along a chain. The six [NCNCN](-) ligands lead to a (4)T(1g) ground state for Co(II) which has an unquenched spin-orbit coupling that is reflected in the magnetic properties. Long-range magnetic ordering was not observed in any of these materials.