一种新型三苯胺类空穴传输材料的合成与性能研究

以2，7-二碘-9，9-二甲基芴为原料分别经过Buchwald-Hartwig交叉偶联反应、Ullmann反应，对目标化合物9，9-二甲基N2，N7二苯基N2，N7二-对甲苯基-9H-芴-2，7-二胺（d-TPA）进行合成研究。通过¹H NMR、¹³C NMR以及HRMS-ESI等表征方法确定结构的正确性。研究表明：以铜粉为催化剂的Ullmann反应收率为85%，是最高效的合成方法。通过X射线衍射（XRD）测试和循环伏安法（CV）测试，结果表明：该材料为非晶材料，成膜性较好，且目标化合物的HOMO轨道能级值为-5.23 eV，与常用阳极材料ITO功函相近且化学稳定性较好，有利于空穴由阳极向空穴传输层的注入。将目标化合物用作空穴传输材料制备了有机发光二级管（OLED）并进行性能测试表征，结果显示：所得器件的启亮电压为3.8 V，最大发光亮度为21 412 cd/m²，最大电流效率为4.78 cd/A，表明该化合物有望成为一种性能优异的新型空穴传输材料。     

Solution‐processable and electroactive aromatic polyamides with 3,5‐bis(trifluoromethyl)triphenylamine moiety

New fluorine‐containing, triphenylamine‐based diamine and dicarboxylic acid monomers, namely 3,5‐bis(trifluoromethyl)‐4′,4″‐diaminotriphenylamine and 3,5‐bis(trifluoromethyl)‐4′,4″‐dicarboxytriphenylamine, were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides, 5a–h and 7a–e . Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, flexible and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass transition temperatures of 273–305 °C and 10% weight‐loss temperatures in excess of 500 °C. Cyclic voltammograms of films of polymers 5a–h on indium–tin oxide‐coated glass substrates exhibited reversible oxidation redox couples with E_1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues. © 2017 Society of Chemical Industry     

Synthesis of Poly(arylene vinylene)s Containing Carbazole,Triphenylamine, and Phenothiazine Rings in the Backbone by Cascade Suzuki-Heck Reactions

Three new conjugated poly(arylene vinylene) structures containing triphenylamine, carbazole, or phenothiazine as aromatic units in the main chain and connected by vinyl segments have been synthesized by a cascade Suzuki-Heck reactions. The best reaction yields were obtained by coupling of the dibromoarylamines with vinyl segments via Suzuki-Heck reaction cascade using Pd(OAc)₂ as catalyst and triethylamine as solvent. The polymers were obtained as fully or partially soluble materials in chlorinated or aprotic polar solvents. They were characterized by ¹H-NMR, FT-IR, UV-Vis, and photoluminescence spectroscopy. Cyclic voltammetry characteristics were studied in solution and as solid thin films deposited on the electrode surface.     

微波辐射合成4-溴-4＇,4″-二甲基三苯胺

以氢氧化钾（4）为缚酸剂,CuCl、1,10-菲啰啉（3）为催化剂,在微波辐射条件下,对碘甲苯（1）和对溴苯胺（2）在甲苯（5）中反应合成了4-溴-4＇,4″-二甲基三苯胺,其结构经1HNMR和IR表征。由正交实验确定最佳工艺条件为：1用量为24 mmol,n（1）∶n（2）∶n（3）=2.4∶1.0∶4.0,微波功率为250 W,于105℃反应120 min,收率77.1%。     

A Bipolar Host Material Containing Triphenylamine and Diphenylphosphoryl‐Substituted Fluorene Units for Highly Efficient Blue Electrophosphorescence

Highly efficient blue electrophosphorescent organic light‐emitting diodes incorporating a bipolar host, 2,7‐bis(diphenylphosphoryl)‐9‐[4‐(N,N‐diphenylamino)phenyl]‐9‐phenylfluorene (POAPF), doped with a conventional blue triplet emitter, iridium(III) bis[(4,6‐difluoro‐phenyl)pyridinato‐N,C^2´]picolinate (FIrpic) are fabricated. The molecular architecture of POAPF features an electron‐donating (p‐type) triphenylamine group and an electron‐accepting (n‐type) 2,7‐bis(diphenyl‐phosphoryl)fluorene segment linked through the sp³‐hybridized C9 position of the fluorene unit. The lack of conjugation between these p‐ and n‐type groups endows POAPF with a triplet energy gap (E_T) of 2.75 eV, which is sufficiently high to confine the triplet excitons on the blue‐emitting guest. In addition, the built‐in bipolar functionality facilitates both electron and hole injection. As a result, a POAPF‐based device doped with 7 wt% FIrpic exhibits a very low turn‐on voltage (2.5 V) and high electroluminescence efficiencies (20.6% and 36.7 lm W^?1). Even at the practical brightnesses of 100 and 1000 cd m^?2, the efficiencies remain high (20.2%/33.8 lm W^?1 and 18.8%/24.3 lm W^?1, respectively), making POAPF a promising material for use in low‐power‐consumption devices for next‐generation flat‐panel displays and light sources.     

Synthesis,characterization and (electro)chemical polymerization of triphenylamine‐end‐functionalized poly(ε‐caprolactone)

Triphenylamine‐based oligomers and polymers with linear, hyperbranched, star‐shaped or dendrimer architectures have been synthesized and studied due to their interesting electro‐optical properties. In many cases insoluble materials are obtained. In this study, we report the synthesis of grafted polytriphenylamine by chemical and electrochemical polymerization of triphenylamine‐end‐functionalized poly(ε‐caprolactone). Functionalized ε‐caprolactone oligomers were obtained by ring‐opening polymerization of ε‐caprolactone initiated by 4‐hydroxymethyltriphenylamine/stannous octanoate (tin 2‐ethylhexanoate). The ring‐opening polymerization of ε‐caprolactone using 4‐hydroxymethyltriphenylamine/stannous octanoate as initiating system provided ε‐caprolactone oligomers, with well‐defined molecular weights, containing a triphenylamine terminal group. Chemical and electrochemical coupling oxidation of the triphenylamine ends allowed the formulation of polyarylamines with ε‐caprolactone oligomers as grafts. Graft copolymers with an aryleneamine backbone and short poly(ε‐caprolactone) grafts were obtained by (electro)chemical oxidation of oligomers containing triphenylamine terminal groups. Copyright © 2009 Society of Chemical Industry     

Novel poly(arylene ethynylene) derivatives containing main chain triphenylamine and pendent quinoxaline moieties: synthesis and elementary characterization

BACKGROUND: Various poly(arylene ethynylene)s (PAEs) have been prepared and applied as molecular wires, in sensors, in nonlinear optics and as electroluminescent materials. But, to our knowledge, there has been no attention paid to the investigation of conjugated PAEs containing both triarylamine and quinoxaline groups. The influence imparted by the introduction of triarylamine and quinoxaline on the photophysical and electrochemical properties of PAEs is of interest. RESULTS: Two kinds of novel PAE derivatives, with electron‐donating triphenylamine groups in the backbone and electron‐accepting pendent quinoxaline moieties and bearing side chains of different lengths, were successfully synthesized with the Sonogashira coupling reaction. These polymers are soluble in common organic solvents and exhibit good film‐forming ability and thermal stability. UV‐visible investigations indicate that the ground states of these materials are unaffected by the polarity of their medium. An efficient intramolecular charge transfer effect is observed from an investigation of their photoluminescence properties in different solvents. Cyclic voltammetry study reveals that these polymers possess relatively high highest occupied molecular orbital levels due to the incorporation of triphenylamine segments into the polymer backbones. CONCLUSION: Primary characterization of these novel PAE derivatives shows that they might serve as potential active materials in optoelectronic devices. Copyright © 2009 Society of Chemical Industry     

Anionic triphenylamine‐ and fluorene‐based conjugated polyelectrolyte as a hole‐transporting material for polymer light‐emitting diodes

BACKGROUND: Hole‐transport layers (HTLs) play a crucial role in multilayer polymeric light‐emitting diodes (PLEDs) for the achievement of satisfactory device performance. During the fabrication of multilayer PLEDs via solution processing, the fabricated HTLs encounter the risk of erosion during the film‐forming process of subsequent emitting layers (EMLs). In contrast to the widely investigated crosslinkable HTLs, much less attention has been paid to the preparation of polar‐solvent‐soluble HTLs, which is a straightforward solution to overcome the interfacial mixing between HTLs and EMLs during solution processing. RESULTS: Alternating triphenylamine‐ and fluorene‐based anionic copolymer poly[9,9‐bis(4′‐sulfonatobutyl)fluorene‐alt‐N‐(p‐trifluoromethyl)phenyl‐4,4′‐diphenylamine]sodium salt (PFT‐CF3) was synthesized via a palladium‐catalyzed Suzuki coupling reaction. This polyelectrolyte is soluble only in polar solvents such as methanol, dimethylformamide and dimethylsulfoxide rather than in non‐polar solvents such as toluene, chloroform and xylene. The relatively high HOMO (?5.22 eV) and LUMO (?2.26 eV) levels of this polymer endow it simultaneously with good hole‐transporting and electron‐blocking capabilities. The performance of red‐, green‐ and blue‐emitting devices utilizing this polyelectrolyte as HTL was investigated. CONCLUSION: The anionic conjugated polyelectrolyte based on triphenylamine and fluorene, PFT‐CF₃, can serve as a promising hole‐transporting/electron‐blocking layer in multilayer PLEDs. Copyright © 2009 Society of Chemical Industry     

电荷传输材料1-(4-甲氧基)苯基-2-[4′-(4″-甲氧基)三苯胺基]-乙烯的合成

在氮气保护下,以二苯胺、对碘苯甲醚和对甲氧基氯苄为原料,经过改良的Ullmann反应、Vilsmeier-Haack反应和Wittig反应,最终合成了电荷传输材料1-(4-甲氧基)苯基-2-[4′-(4″-甲氧基)三苯胺基]-乙烯,并优化了反应条件。该合成工艺具有反应温度低、反应时间短、操作简单的优点。     

具有D-π-A结构的三苯胺衍生物的合成及其性能

以三苯胺、5-醛基-2-噻吩硼酸、丙二腈为主要原料,合成了一种具有D-π-A结构的三苯胺衍生物2-[5-[4-(N,N-二苯氨基)苯基]噻吩基]亚甲基丙二腈(DPTM)。通过FTIR、1H NMR和元素分析对该化合物的结构进行了表征,考察了其UV-Vis光谱、荧光光谱、电化学行为和热稳定性。研究结果表明,DPTM具有溶液成膜性,DPTM的二氯甲烷溶液及其固态薄膜均显示出很强的红色荧光,荧光量子产率为79.15%;DPTM的HOMO能级为-5.51 eV,与正电极的功函数(-4.8 eV)相匹配,可有效降低空穴注入的能垒,有利于空穴的注入和传输;DPTM的热分解温度为182℃,具有良好的热稳定性。DPTM有望作为一种具有空穴传输性能和发光性能的新型红色发光材料。