一种主链含有离子导电性链段的功能发光共聚物

1990年英国剑桥大学的Ｂｕｒｒｏｕｇｈｅｓ等人[1 ]使用聚对苯乙炔 (ＰＰＶ)成功的制备了第一个聚合物电致发光二极管 (ＬＥＤ)的报道引起了电致发光领域世界范围内的研究高潮 ,特别是 1 995年裴启兵等人[2 ,3] 发明的电化学发光电池 (ＬＥＣ)的技术更进一步地推动了聚合物发光器件商业化的步伐。ＬＥＣ相对于ＬＥＤ具有很多优势[4] ,但是ＬＥＣ中一个关键技术是要克服共轭非极性荧光聚合物与非共轭极性离子传导聚合物的相分离问题从而制备高质量的发光薄膜 .目前较好的解决方法是将极性的离子传导侧链接枝在荧光聚合物的主链上而得到直接…     

聚(对苯撑乙烯)发光材料

带有共轭键结构的聚合物材料是近几年来有机光电子材料领域中最为活跃的研究课题之一,其原因主要有:(1)通过共轭链骨架上取代基的修饰或者通过控制共轭链的长度,可得到不同波长的发射光,如无机材料难以实现的蓝光;(2)能溶于一般的有机溶剂,因此薄膜制备工艺简单、成膜性好;(3)可制备大面积发光层,成本低。这些特点使聚合物发光材料向实际应用迅速发展。     

一种合成聚(2-甲氧基-5-(2′-乙基-己氧基)-对苯乙炔)的新方法

聚对苯乙炔 (ＰＰＶ)及其衍生物是制备聚合物发光二极管的最重要的聚合物之一[1] .这主要是因为它们具有优越的电致发光性能 ,易于合成以及良好的环境稳定性[2 ] .而聚 (2 甲氧基 5 (2′ 乙基 己氧基 ) 对苯乙炔 ) (ＭＥＨ ＰＰＶ)由于其可溶性好 ,发光效率和亮度高 ,在电致发光领域广受关注 .现在有许多ＭＥＨ ＰＰＶ的多步化学合成方法以及电化学合成方法 .但是 ,这些方法常常产率低 ,成本高且产品不纯 .本文报道一种固 液两相反应一步合成分子量大、溶解性好的ＭＥＨ ＰＰＶ的新方法 .1　主要原料对甲氧基苯酚 (纯度≥ 98% ,Ａｌｄｒ…     

带有PPE侧链的聚合物的合成及其发光性质的研究

有机共轭聚合物发光材料成为近年来多学科交叉研究的热点[1~3]。作为共轭聚合物之一,聚对苯乙炔(Poly(p-phenyleneethynylene))(PPE)具有较高的电子亲合势、电致发光效率、对微量水和氧气稳定等优点,近年来受到很大的关注[4~7]。PPE分子链间通过π-π堆积效应(π-πstacking)在     

电致发光聚合物/纳米半导体材料及其双功能器件

电致发光材料在大屏幕平板显示和移动通讯器件方面有着极大的优越性。Ⅱ-Ⅵ族无机半导体、金属有机化合物及共轭聚合物等都是电致发光材料。由半导体纳米晶体和电致发光聚合物组成的双发光器件中,纳米半导体的发光不仅可以通过掺杂及形成核壳结构来加以调节,而且受到其复合体系类型、纳晶含量、外加电压等因素制约;而无机半导体的高电荷输运特性也将影响聚合物发光层的效率。同时,利用无机纳米半导体的光导特性,这种复合体系也可以制成光导与电致发光双功能器件,且其发光效率可有较大幅度提高。     

稀土有机光→电、电→光转换器件

198 6年Ｔａｎｇ发表双层有机光伏电池[1] 与无机光伏电池相比 ,以重量轻 ,材料经济并可以沉积在柔性衬底上等潜在优势正在引起人们注意。目前对有机光伏效应的研究多集中在聚苯乙炔 (ＰＰＶ)及其衍生物上[2 ,3 ] ,能量转换效率在 10ｍＷ·ｃｍ- 2 紫外光照下可超过 4 % [4 ] ;以小分子有机物制成的光伏器件也得到研究人员的关注[5,6] 。但是采用稀土配合物作为电子给体层的有机光伏器件还未见报道。我们研究组一直对以稀土有机配合物为发光层的有机ＥＬ器件进行研究[7,8] 。在研究ＥＬ器件特性过程中 ,我们发现稀土有机电致发光器件在紫外…     

含噁二唑的聚(间亚苯乙烯)电致发光二极管

1990年英国剑桥大学的Burroughes等人[1]以聚(对亚苯乙烯)为发光材料制备了第一个有机聚合物电致发光二极管,该工作引起了科学工作者的极大兴趣.聚合物材料具有很好的电、热稳定性以及机械加工和成膜性能,发光亮度和效率较高,通过化学修饰可获得三原色发光.而且聚合物电致发光二极管的工作电压较低,可实现大面积平板显示和集成化.     

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。     

一种超支化聚硅烷的合成和性能

近年来,光电高分子的研究由于其在发光二极管、太阳能电池、光信息材料、传感器等方面的潜在应用而得到了广泛重视[1].自从英国剑桥大学Cavendish实验室的Burroughes等首次发现聚对亚苯基亚乙烯基的电致发光现象以来[2],共轭聚合物作为发光材料的研究迅速引起了人们的注意[3~5]     

主链含PEO链段的聚对苯乙炔类蓝色电致发光共聚物

采用Ｗｉｔｔｉｇ反应合成了一种分子主链上烷氧基取代刚性共轭聚对苯乙炔（ＰＰＶ）民柔性聚氧化乙烯（ＰＥＯ）链段交替排列的、可溶于氯仿与四氢呋喃等普通有机溶剂的新型结构的聚对苯乙炔类功能性发光共聚物ＥＯ－ＰＰＶ。采用ＦＴ－ＩＲ、＾１Ｈ－ＮＭＲ、ＤＳＣ、ＧＰＣ、元素分析等手段对共聚物进行了表征,并制备了结构为（Ａｌ）Ｃａ／ＥＯ－ＰＰＶ／ＩＴＯ的单层电致发光器件、器件的最大发光波长位于４７５ｎｍ（蓝光）。     

Molecular engineering in symmetric end-substituted oligothiophene derivatives: analysis of condensed-phase photoemission spectra using semiempirical Hartree-Fock calculations

The electronic structures of two series of end-capped thiophene oligomers, one set containing the electron-deficient dimesitylboryl end-cap and one containing the electron-rich triaryl amine end-cap, have been modeled using semiempirical quantum chemical calculations and the results used to assign features in the photoemission spectra of the materials in the condensed phase. For the thiophene oligomers end-capped with the electron-deficient dimesitylboryl moieties, the energy of the occupied frontier orbitals is largely governed by pi-type orbitals of the thiophene repeat units in the oligothiophene main chain. Conversely, in oligomers end-capped with electron-rich triarylamine moieties, the occupied frontier orbital energies are largely governed by orbital states of heavily mixed character associated with thiophene pi-type systems and the low-lying nitrogen lone pairs of end capping groups.     

Inclusion complexation of cyclobis(paraquat-p-phenylene) with thiophene, bithiophene and terthiophene

The inclusion complexation between the electron-poor cyclophane, i.e. cyclobis(paraquat-p-phenylene), and the electron-rich thiophene oligomers, i.e. thiophene, bithiophene and terthiophene, were characterized in solution and solid state. In solution, we confirmed a 1:1 complexation and that the binding strength depends on the number of the thiophene units. From the X-ray crystallographic analysis we confirmed the solid-state structure of the inclusion complex. These results indicate that charge-transfer, π–π and van der Waals interactions may contribute to the driving force of inclusion complexation.     

Direct Carboxylation of Electron-Rich Heteroarenes Promoted by LiO-tBu with CsF and [18]Crown-6

We herein demonstrate that the combination of LiO-tBu, CsF, and [18]crown-6 efficiently promotes the direct C−H carboxylation of electron-rich heteroarenes (benzothiophene, thiophene, benzofuran, and furan derivatives). A variety of functional groups, including methyl, methoxy, halo, cyano, amide, and keto moieties, are compatible with this system. The reaction proceeds via the formation of a tert-butyl carbonate species.     

5,5-Fused thiophene gamma-lactams as templates for serine protease inhibition

Novel 5,5-fused thiophene lactams are potent inhibitors and acylating agents of HNE and PPE.     

A phenylenevinylene‐thiophene‐phenyleneethynylene copolymer: synthesis,characterization, and photovoltaic properties

A phenylenevinylene‐thiophene‐phenyleneethynylene copolymer, poly{[1′,4′‐bis‐(thienyl‐vinyl)]‐2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene‐vinylene‐alt‐1,4‐dioctyloxyl‐phenyleneethynylene}(PTPPV‐ PPE), was synthesized by the Sonogashira Pd‐catalyzed cross‐coupling reaction. The copolymer possesses higher thermal decomposition temperature (T_d = 382°C) compared with poly{[1′,4′‐bis‐ (thienyl‐vinyl)]‐2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene‐vinylene} (PTPPV). The absorption and photoluminescence (PL) peaks of PTPPV‐PPE solution and solid film locate in between those of the homopolymers of PTPPV and poly(1,4‐dioctyloxyl‐phenyleneethynylene) (PPE), and closer to that of PTPPV. Photovoltaic cell was fabricated based on the blend of PTPPV‐PPE and PCBM with a weight ratio of 1:1. The primary result shows an open circuit voltage (V_oc) of 0.72 V which is higher than that of the PTPPV (0.67 V), and a power conversion efficiency (PCE) of 0.3% under the illumination of AM1.5, 100 mW/cm² which is much better than that of PPEs. Copyright © 2008 John Wiley & Sons, Ltd.     

Catalytic asymmetric cyclopropanation of heteroaryldiazoacetates

Rh(2)(S-DOSP)(4)-catalyzed decomposition of heteroaryldiazoacetates in the presence of styrene results in highly diastereoselective and enantioselective cyclopropanations. Heteroaryldiazoacetates containing both electron-rich and electron-deficient heterocycles, such as thiophene, furan, pyridine, indole, oxazole, isoxazole, and benzoxazole, are effective in this chemistry. These studies broaden the range of diazo compounds containing both electron-withdrawing and electron-donating groups, which undergo highly diastereoselective cyclopropanations.     

RhIII-Catalyzed C6-Selective Oxidative C−H/C−H Crosscoupling of 2-Pyridones with Thiophenes

A rhodium(III)-catalyzed C6-selective dehydrogenative cross-coupling of 2-pyridones with thiophenes was developed for the synthesis of 6-thiophenyl pyridin-2(1H)-one derivatives. In this reaction, the excellent site selectivity was controlled by the 2-pyridyl directing group on the nitrogen of the pyridone ring. Control experiments indicated that the N-pyridyl was essential for the transformation. To the best of our knowledge, this procedure is the first successful example of the direct C6 heteroarylation of 2-pyridones with electron-rich thiophene derivatives. 4-Pyridone was also used as substrate to generate the corresponding C2 heteroarylated product. Moreover, this pyridyl directing group was readily removable to generate the biheteroaryl structures with a free N−H group.     

Preparation of poly(phosphate ester)s having bisphenol moieties as mesogenic units in the main chain

Poly(phosphate ester)s, PPE 1a–d , were synthesized from polycondensation of methyl phosphorodichloridate (MPDC) with various bisphenols such as 4,4′-biphenol 1a , 4,4′-dihydroxyphenylether 1b , bis(4-hydroxyphenyl)methane 1c , and 3,3′-dimethyl-4,4′-dihy-droxybiphenyl 1d . PPE 2a–d with hexamethylene spacers were also obtained from poly-condensation of MPDC with 4,4′-bis(6-hydroxyhexyloxy)biphenyl 2a , 4,4′-di(6-hydroxyhexyloxy)phenyl ether 2b , bis[4-(6-hydroxyhexyloxy)phenyl]methane 2c , and 3,3′-dimethyl 4,4′-di(6-hydroxyhexyloxy)biphenyl 2d . The degree of crystallinity of PPE 1a–1d without hexamethylene spacer was 3.3–17.6%, whereas PPE 2a and PPE 2b which exhibit mesomorphic behavior were 20.1 and 18.6%, respectively. PPE 2a and PPE 2b show the mesophase at 139.6–195.5°C and 42.4–66.3°C, respectively. PPE 2c and PPE 2d were obtained as rubbery. From pyrolysis of PPE in air the temperature corresponding to 5% weight loss was found to be 322–408°C and 284–291°C for PPE 1 and PPE 2 , respectively. It was also found that PPE 2a was enzymatically degraded by phospholipase C. © 1994 John Wiley & Sons, Inc.     

Novel Bis-arylPheDOT Synthons for Electrochromic Polymers

Two terthiophenes incorporating the synthon 3,4-(1,2-phenylenedioxy)thiophene (PheDOT) have been developed. Specifically, 2,5-bisthienyl-3,4-(1,2-phenylenedioxy)thiophene (BTh-PheDOT 1) and 2,5-bisethylenedioxythienyl-3,4-(1,2-phenylenedioxy)thiophene (BEDOT-PheDOT 2) were electropolymerized to form electroactive polymer films (P1 and P2) that switched between two highly colored states with the more electron-rich EDOT derivative P2 observed to switch at a lower potential. Additionally, both P1 and P2 displayed moderate to low optical bandgaps of 1.8 and 1.6 eV, respectively. Crystal structures of BTh-PheDOT showed the monomer to be nearly planar with π -stacking observable between monomers. These findings demonstrate the potential of PheDOT as an electroactive synthon for the formation of well-ordered systems.     

Two-photon absorption in V-type chromophores with electron-rich heterocyclevinylene bridges

A series of V-type chromophores with electron-rich heterocyclevinylene bridges have been synthesized via Wittig-Horner-Emmons and Vilsmeier reactions.All the target chromophores showed strong one-photon and two-photon excited emission,and their electron properties could be tuned by using different heterocycles such as furan,thiophene and pyrrole moieties in I-III.The maximum two-photon absorption (TPA) cross sections occurred at 760 nm and were measured to be in the range of 400-800 GM.