聚芴类电致发光材料的研究进展

聚芴衍生物是最有发展潜力的电致发光材料之一。本文从聚芴衍生物的结构出发,概述了通过化学方法对聚合物的性能进行优化的最新研究进展,着重于发光效率和发光稳定性、发光颜色、加工性能的改善方法。     

聚合物电致发光材料及其发光颜色调节的研究进展

聚合物电致发光材料已成为功能材料研究领域的一个热点.与无机材料和有机小分子材料相比,聚合物发光材料具有来源广泛、易加工成型、通过分子结构设计可调节发光颜色等优点,成为制备大面积、低成本、全色柔性显示器件的首选材料.本文介绍了聚合物发光材料的发光机理及调节发光颜色的常用方法,综述了聚对苯乙炔类、聚对苯类、聚芴类等多种共轭聚合物发光材料的合成及发光颜色调节的研究现状,并对聚合物发光材料的发展趋势以及聚合物电致发光器件的制备进行了评述和展望.     

用于电致发光器件的蓝光聚合物材料研究进展

聚合物电致发光材料成型加工简便、可大面积生产,可应用于大面积平板显示及固体照明器件。与红、绿光聚合物发光材料相比,蓝光聚合物电致发光材料在发光性能、材料寿命等方面仍然存在较大差距,这成为全色显示的瓶颈。通过在聚合物主链上引入大体积的取代基或侧链、形成具有三维空间共轭效应的支化结构或能量可转移的主客体结构等,来改善溶解性和光物理性能等,从而得到发光效率高、色纯度好、热力学性能优异且材料加工性能良好的蓝光聚合物电致发光材料。本文从材料设计的角度简要介绍了国内外蓝光聚合物发光材料的主要研究进展。     

芴与噻吩发光共聚物的合成及其电致发光性能

采用Suzuki偶合方法合成出了一系列新型的 9,9 二辛基芴 (DOF)和噻吩 (Th)的共聚物 .其中 ,DOF与Th的投料比 (摩尔比 )分别为 95∶5 (PTF5 )、90∶1 0 (PTF1 0 )、85∶1 5 (PTF1 5 )、70∶3 0 (PTF3 0 )、5 0∶5 0 (PTF5 0 ) .所有的聚合物均可溶于常用的有机溶剂 ,如THF,CHCl3等 ,其分子量在 60 0 0～ 5 3 0 0 0之间 .当在聚芴主链中引入噻吩后 ,其发光波长发生了红移 ,最大发光波长由PTF5时的 490nm红移到PTF5 0时的 5 41nm .随着聚芴主链中噻吩含量的增加 ,最大电致发光和光致发光效率都逐渐降低 由这些聚合物所制得的器件 ,最大电致发光效率为PTF5和PTF1 0的 0 45 %.由此表明 ,在聚芴主链中引入少量的低带隙单体噻吩可以调节聚芴的发光颜色及发光效率     

几种电致发光聚合物材料的研究进展

介绍了几种典型的电致发光聚合物材料,包括聚(对苯乙烯撑)及其衍生物、聚噻吩及其衍生物、聚芴及其衍生物,对它们的结构、制备方法、特点进行了归纳和讨论。其中最重要的是聚(对苯乙烯撑)(PPV)及其衍生物,目前采用较多的制备方法是前聚物法和强碱诱导的去卤缩合法以及电化学聚合法。在苯环上引入长链烷烃、烷氧基或芳基后的取代PPV,即PPV的衍生物,可溶于很多有机溶剂。可溶性PPV衍生物为制备多层电致发光聚合物器件提供了有效途径。文章还对电致发光聚合物材料存在的问题和发展前景进行了探讨和展望。     

末端含蓝光发色团的超支化聚苯材料的合成

在聚合物发光材料研究领域中,作为三元色之一的蓝色发光材料的设计与合成倍受关注．一维线型结构的聚对苯及聚烷基芴等是典型的蓝色发光材料;线型结构的聚对亚苯亚乙烯基(PPV)及聚对亚苯亚乙炔基(PPE)具有电子流动性好,在溶液中有高荧光量子效率也可衍生得到蓝色发光材料,这主要是在共轭聚合物主链上嵌入非共轭部分,     

侧链接枝低聚对亚苯基亚乙烯基聚芴衍生物的合成及其电致发光性能

采用Wittig-Horner反应,将少量端基为磷脂的黄光发射客体低聚对亚苯基亚乙烯基链段(MOPV)接枝到含有醛基单体的蓝光发射主体材料聚芴的侧链上,合成了一种新型的接枝聚芴衍生物PF-g-MOPV.这种接枝聚合物具有很好的热稳定性,可溶于常用的有机溶剂.以接枝共聚物PF-g-MOPV为发光层的单层器件发射出黄绿光,色坐标为(0.30,0.57),最大发光亮度达到1550cm/m2,这说明蓝光聚芴主链向侧链MOPV进行了有效地能量转移.     

三苯基吡啶-芴交替共轭聚合物的合成与光致发光性能研究

通过Suzuki偶合反应得到了两种间位连接的三苯基吡啶同分异构体和9,9-二辛基芴的交替共聚物PFOTPP1和PFOTPP2.并对它们的紫外-可见吸收光谱、光致发光光谱以及电化学性能等进行了初步研究.结果表明,将间位连接的三苯基吡啶基引入聚芴主链能使聚合物的LUMO能级降低,光致发光光谱发生蓝移,得到了两种有望应用于电致炼光发光器件的共轭聚合物蓝光发光材料.     

聚合物光电功能材料的合成与器件探索

在本实验室以前工作的基础上,利用Wittig反应和Wittig-Horner反应,合成了含有三苯胺单元的交替共聚物,它们具有良好的溶解性、成膜性和热稳定性,是一类具有较高效率的发绿光材料.通过在聚合物中引入芴和联苯的结构以及在PPV单元上引入不同链长的侧基等,研究了聚合物的几何构型以及位阻等因素对材料性质的影响.通过三元共聚研究了聚合物链中三苯胺含量对发光性能的影响,其中以三苯胺、PPV和二甲氧基PPV组成的三元共聚物在聚合物LED中得到了良好的电致发光性能.     

吡啶-芴类电荧光聚合物的光谱特性

用Suzuiki聚合反应将二溴代吡啶 (2 ,5 、2 ,6 、3,5 取代 )与芴共聚 ,合成了不同主链结构的吡啶 芴共聚物 .研究结果表明 ,将吡啶基引人聚芴主链可以调节共聚物的发光颜色 .间位吡啶基引入聚芴主链 ,使聚合物的能级加宽 ,PL、EL光谱发生蓝移 ;对位吡啶基则使光谱红移 .间位吡啶基 (3,5 Py、2 ,6 Py)引入聚芴主链 ,可提高聚合物的色纯度 .共聚物中 3,5 Py含量为 4 0mol%时 ,可得到较纯的蓝光 .     

Liquid crystalline conjugated polymers and their applications in organic electronics

This article describes the syntheses and electro‐optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p‐phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p‐phenylenevinylene)s, the Suzuki‐ or Yamamoto‐coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main‐chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side‐chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field‐effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo‐fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713–2733, 2009     

Fluorescent aromatic polyamides with urea binding sites and fluorene or dansyl signaling units

This work describes six novel fluorescent aromatic polyamides with bulky dansyl or fluorene pendant groups or with the fluorene moiety in the main chain. The fluorescent signaling dansyl or fluorene moieties are chemically connected to, or within, the main polymer chains through a urea group, a well-known binding site in supramolecular chemistry. These polyamides are amorphous and soluble in polar aprotic solvents and demonstrate a film-forming capability. They also show yellowish-green or blue fluorescence in solution and in the solid state depending on the signaling unit, with the former corresponding to the dansyl and the latter to the fluorene residue. The water uptake and the thermal behavior have also been evaluated and related to the chemical structure. The polar amide, urea, and sulfonamide groups give rise to a high water sorption of up to 3.8 water molecules per repeating unit. The thermal behavior has been investigated by means of DSC and TGA. The glass transition temperatures of the polymers are high (up to 331 °C) and the decomposition temperatures (around 300 °C) are due to the moderate thermal stability of the urea group.     

Synthesis,characterization, and electroluminescence of fluorene and carbazole‐based blue light‐emitting polymers with different noncoplanar molecular architectures

In order to investigate the explicit optoelectronic variations of the photoluminescent polymer with sterically hindered side chains, three novel alternate polymers (P0, P1, and P2) based on fluorene and carbazole moieties were successfully synthesized through Suzuki coupling reaction. The molecular structures of the polymers were fully characterized by ¹H‐NMR, ¹³C‐NMR, elemental analysis, and gel permeation chromatograph, respectively. The photophysical properties, thermal stability, and energy band gaps of polymers P0, P1, and P2 were further examined through UV–vis absorption, photoluminescent spectra, differential scanning calorimetry, thermogravimetric analysis, and cyclic voltammetry. The experimental results indicated that the polymers took on wide band gaps of about 3.50 eV with deep blue emission in thin solid films. These polymers were found to show a high thermal stability with decomposition temperatures at 5% weight loss of the compounds in the range of 353–416 °C. Blue light‐emitting electroluminescent devices of the most branched polymer P2 with highest light‐emitting efficiency as emitting layers were characterized, which showed obviously improved spectral stabilities with respect to the parent polyfluorene materials. In conclusion, we have established an effective method to improve the spectral stabilities of polyfluorene material by synthesizing the zigzag‐shaped copolymer of fluorene and carbazole with sterically hindered pendant moieties of different molecular sizes. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical Upcycling of Conventional Polyureas into Dynamic Covalent Poly(aminoketoenamide)s

The chemical upcycling of polymers is an emerging strategy to transform post-consumer waste into higher-value chemicals and materials. However, on account of the high stability of the chemical bonds that constitute their main chains, the chemical modification of many polymers proves to be difficult. Here, we report a versatile approach for the upcycling of linear and cross-linked polyureas, which are widely used because of their high chemical stability. The treatment of these polymers or their composites with acetylacetone affords di-vinylogous amide-terminated compounds in good yield. These products can be reacted with aromatic isocyanates, and the resulting aminoketoenamide bonds are highly dynamic at elevated temperatures. We show here that this conversion scheme can be exploited for the preparation of dynamic covalent poly(aminoketoenamide) networks, which are healable and reprocessable through thermal treatment without any catalyst.     

High-efficiency red-light emission from polyfluorenes grafted with cyclometalated iridium complexes and charge transport moiety

We report a new route for the design of electroluminescent polymers by grafting high-efficiency phosphorescent organometallic complexes as dopants and charge transport moieties onto alky side chains of fully conjugated polymers for polymer light-emitting diodes (PLED) with single layer/single polymers. The polymer system studied involves polyfluorene (PF) as the base conjugated polymer, carbazole (Cz) as the charge transport moiety and a source for green emission by forming an electroplex with the PF main chain, and cyclometalated iridium (Ir) complexes as the phosphorescent dopant. Energy transfer from the green Ir complex or an electroplex formed between the fluorene main chain and side-chain carbazole moieties, in addition to that from the PF main chain, to the red Ir complex can significantly enhance the device performance, and a red light-emitting device with the high efficiency 2.8 cd/A at 7 V and 65 cd/m2, comparable to that of the same Ir complex-based OLED, and a broad-band light-emitting device containing blue, green, and red peaks (2.16 cd/A at 9 V) are obtained.     

Progress in long wavelength emission in fluorene-based electroluminescent blue materials

On account of the advantages of organic electroluminescent materials compared with their inorganic counterparts,the development of organic electroluminescent materials is one of the hot areas of the optoelectronic materials.Fluorene and its derivatives,which have an aromatic biphenyl structure with a wide energy gap in the backbones and high luminescent efficiency,have drawn much attention of ma-terial chemists and device physicists.However,one drawback of fluorene-based electroluminescent blue materials is that there is an occurrence of long wavelength emission after annealing the films in air or after operating organic light-emitting diodes for a long time.To clarify the origin of this long wave-length emission,the scientists at home and abroad have put forward all kinds of correlative explana-tions.Among the scientists,some thought it was caused by excimer-related species,while some others claimed that it was caused by the fluorenone of photooxdized fluorene.The corresponding solutions to this problem have also been proposed and the problem has been partially resolved in some degree.The present review summarizes and analyzes the progress made on the origin of long wavelength emission in fluorene-based electroluminescent blue materials at home and abroad in the past few years.Some issues to be addressed and hotspots to be further investigated are also presented and discussed.     

Chemical modification of the pendant structure of wholly aromatic polyamides: Toward functional high‐performance materials with tuned chromogenic and fluorogenic behavior

This work describes the preparation of functional aromatic polyamides with pendant fluorescent chemical structures. The preparation of a parent copolyamide with a lateral fluorene moiety anchored to the main chain through a urea group is described, along with the chemical modification of the fluorene moieties to render six copolymers with different fluorescent behaviors. The easy and clean chemical modification of the polyamide structure permits the preparation of high‐performance materials with “a la carte” fluorescence properties. The characteristics of these materials make them useful for cutting‐edge technologies associated with the fluorescence of the pendant fluorene moiety and with the host behavior of the urea motif, that is, fluorescent sensing of analytes or hybrid luminescent converter—light‐emitting diode systems. The chemical modification of the polymer structure was carried out with chemicals and conditions optimized for polyamide models. The influence of the chemical structure of the pendant fluorene core has also been addressed in terms of thermal properties, solubility, water uptake, and so forth. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3823–3833, 2010     

Synthesis of fusible and soluble conducting polyfluorene derivatives and their characteristics

Conducting polyfluorene derivatives with alkyl chains—poly(9-alkylfluorene)s and poly-(9,9-dialkylfluorene)s—have been synthesized by chemical polymerization utilizing FeCl₃ as an oxidizing agent. The polymers obtained are found to be soluble in conventional organic solvents such as chloroform and have been characterized by ¹H- and ¹³C-NMR. The results indicate that the fluorene moeities are mainly linked in the 2,7′-fashion to yield the straight chain polymer. The degree of polymerization is estimated (by gel permeation chromatography) to be of the order of 10. The polymers are found to be fusible and the thermal properties of the polymers have been characterized by differential scanning calorimetry. The glass transition temperature is found to decrease with an increase of the alkyl chain length. © 1993 John Wiley & Sons, Inc.     

Kerr-effect in solutions and molecular polarity of liquid crystalline fluorenes

As part of a broader study of liquid crystal polymers with side groups containing fluorene moieties, more information was required about the properties of fluorene derivatives. With this aim in mind, the solution Kerr-effects for five fluorene-based mesogens have been measured and used in conjunction with other results to determine the polarizability anisotropies and dipole moments.     

Design and synthesis of polymers for light-emitting diodes

Polymers with aromatic ϕ-conjugated moieties were utilized as electroluminescent materials. In order to meet the requirements for light-emitting diodes (LED), the design and synthesis of electroluminescent polymers had to be developed and viewed in this review. Focus is on polymers with arylene vinylene, arylene ethinylene, phenylene, thiophene and arylene amine moieties as light-emitting, hole-transporting and electron-transporting materials in LED devices. An attempt has been made to arrange a structural classification of electroluminescent polymers in nonsegmented and segmented polymers. © 1998 John Wiley & Sons, Ltd.