含柔性链段的苯并二噁唑类聚合物合成与表征

通过溶液缩聚反应,合成了一系列含有刚性苯并唑噁环和柔性脂肪链的刚、柔间隔聚合物.通过FT-IR1H-NMR 和 TGA 等方法对聚合物化学结构和热失重行为进行了表征.发现聚合物分子链中出现了微量未闭环结构,热分解温度有所降低.聚合物溶液的紫外吸收光谱的最大吸收从 PBO 的429 nm蓝移到 PBOC7 的291 nm,同时荧光 stokes 位移增大.     

聚芴基苯并唑类共聚物的合成和光物理性能

通过溶液缩聚法合成了一系列不同组分的无规共聚物--聚对苯撑苯并二噁唑-co-聚(9,9-二辛基芴苯并二噁唑)(PBO-co-PBOF).利用X射线衍射、紫外-可见光吸收光谱、光致荧光光谱研究了不同组分和结构变化对聚合物形态和光物理性能的影响.结果表明:聚合物主链上辛基芴基团的引入使聚合物结构从晶态转变为非晶态.共聚物分...     

含联芴烯单元共轭聚合物的合成及表征

以六羰基钨[W(CO)₆]为催化剂, 合成了聚吲哚芴(P1)、 聚梯型四苯(P2)、 聚梯型五苯(P3)和小分子9-联吲哚芴烯(S1).该类聚合物的重复单元含有联芴烯结构, 通过芴9位的双键连接. 光学和电化学等实验结果表明, 聚合物无荧光发射, 是一类窄带隙的共轭聚合物, 其中聚合物P1薄膜的紫外吸收值最大波长为710 nm.     

含苯并三氮唑单元的聚对苯撑乙炔类聚合物的合成及性能

利用Pd（Ⅱ）配合物为催化剂,使用4,7-二溴-2-十二烷基-1,2,3-苯并三氮唑和1,4-二乙炔基-2,5-二（烷氧基）苯通过Sonogashira反应合成了3个带有不同长度烷氧基侧链,主链中含有1,2,3-苯并三氮唑单元的聚苯乙炔类聚合物。采用FT-IR、1H-NMR对其化学结构进行了表征。结果表明：这类聚合物的数均分子量在0.93×104～1.13×104,苯并三氮唑单元上长链烷基和苯环上长链烷氧基的存在使此类聚合物在CHCl3、THF等溶液中的溶解度较大,其固态薄膜也较容易制备,聚合物在固态薄膜状态下的紫外-可见最大吸收波长比在CHCl3溶液中红移了约45 nm,在固态薄膜状态下的荧光发射峰比在CHCl3溶液中也发生了较大的红移。     

含柔性链段的苯并二啞唑类聚合物合成与表征

通过溶液缩聚反应,合成了一系列含有刚性苯并啞唑环和柔性脂肪链的刚、柔间隔聚合物.通过FT-IR1、H-NMR和TGA等方法对聚合物化学结构和热失重行为进行了表征.发现聚合物分子链中出现了微量未闭环结构,热分解温度有所降低.聚合物溶液的紫外吸收光谱的最大吸收从PBO的429 nm蓝移到PBOC7的291 nm,同时荧光Stokes位移增大.     

PBO聚合物紫外吸收光谱中环境因素影响的理论研究

芳杂环液晶高分子聚对亚苯基苯并二噁唑（PBO, poly(p-phenylene-2,6- benzobisoxazole)）的共轭平面结构赋予其光电性能而备受关注.实验结果表明其光电性能受其所处环境状态影响. 通过量子化学计算研究发现,PBO无论固态还是溶液状态的最大紫外吸收均较其本征值有所红移.对PBO二聚体模型以及其在强质子酸中所具有的质子化形态模型的紫外吸收光谱计算模拟的结果表明,PBO聚集态时的分子间相互作用,以及溶液中质子化效应均导致红移.质子化模型所得紫外吸收光谱能很好地阐释溶液中具有精细结构实测的紫外吸收光谱.     

共轭刚性苯并二噁唑类聚合物的合成及其光物理性能研究

设计并合成了一系列共轭高分子———聚亚苯基苯并二唑 (PBO) ,聚亚乙烯基苯并二唑 (PBOV)和聚亚丁二唑 (PBODV) ,并对它们进行了表征 .用紫外吸收光谱和荧光光谱对聚合物的溶液和薄膜进行了详细的研究 ,研究结果表明分子结构中双键的引入可以降低聚合物的光带能隙 ,λmax从PBO溶液的 4 2 8 5nm (Eg=2 76eV) ,到PBOV溶液的 4 80 5nm (Eg=2 4 6eV) ,再到PBODV溶液的 4 96 0nm (Eg=2 38eV) .共轭程度的增加使得聚合物溶液更容易发生集聚从而导致荧光自熄灭 .     

苯并噻二唑与苯胺类聚合物的金属镍配合物催化法合成与表征

以1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)[Ni(dppp)Cl2]作催化剂,通过4,7-二溴-2,1,3-苯并噻二唑格氏(Grignard)试剂分别与3,3′-二甲基联苯二胺、对苯二胺共聚得到了两种新型主链含刚性和柔性链结构的苯并噻二唑类共轭聚合物。通过FT-IR、1H-NMR、UV-Vis、XRD、TGA等测试手段对聚合物的化学结构和性能进行了表征。结果表明:聚合物的紫外-可见最大吸收波长分别在306 nm和380 nm处出现,荧光激发峰分别出现在378 nm和463 nm,相应的荧光发射峰分别在493、562 nm处出现。共轭聚合物具有一定的结晶性和热稳定性。     

胺烷基侧链取代三苯胺类红光聚合物的合成及性能研究

通过Suzuki偶合反应合成了一系列胺烷基侧链取代的基于三苯胺和芴的共轭聚合物聚[4-(N,N-二甲基胺丙氧基)苯-4,4′-二苯胺-9,9-二辛基芴-4,7-二噻吩-2-基-2,1,3-苯并噻二唑](PFTD), 并对其化学结构和光电性能进行了表征. 末端胺基的存在提高了此类聚合物作为发光层应用于聚合物电致发光器件的性能(采用高功函数的金属铝作为阴极时). 结构为ITO/PVK/PFTD-5(DBT摩尔分数为5%时的聚合物)/Al的器件最大电致发射峰位于647 nm, 最大外量子效率达到了1.24%.     

给体-受体-给体窄带隙染料掺杂聚芴发光二极管

合成了一系列给体-受体-给体型窄带隙荧光分子, 并将其作为掺杂剂与主体(Host)宽带隙聚芴共混制备发光二极管. 荧光分子为4,7-二呋喃-苯并噻二唑(O-S)、4,7-二噻吩-苯并噻二唑(S-S)、4,7-二(N-甲基吡咯)-苯并噻二唑(N-S)、4,7-二硒吩-苯并噻二唑(Se-S)和4,7-二(N-甲基吡咯)-苯并硒二唑(N-Se). 溶液中荧光分子的紫外-可见吸收峰位于447~472 nm, 荧光发射峰位于563~637 nm. 该系列荧光分子掺杂聚芴(PFO)发光器件的电致发光峰位于580~633 nm. 当器件结构为ITO/PEDOT/PVK/PFO+N-Se/Ba/Al时, 最大外量子效率为1.28%, 电流效率1.31 cd/A.     

发蓝光材料聚烷基芴的合成和性能研究

聚芴及其衍生物是一类极具光、电活性的重要有机聚合物材料 .早在 90年代初 ,Fukuda等[1,2 ]首先报道了聚芴的合成 .在过去的几年中 ,由于这类聚合物及其衍生物卓越的光电性能 ,使其在发光二极管、激光器件、导电光刻蚀、光电池、生物传感器件等方面得到了广泛应用 ,从而推动了这一领域的飞速发展 .国外研究者在这方面进行了大量的研究工作 ,合成了一系列具有光电性能的聚芴共聚物 ,并用于研制各种光电器件[3～ 10 ] .从单体合成方法来看 ,大多都有采用文献 [1 ]所述的方法 ,但该方法要求在无水 (正丁基锂 )、无氧 (Ar气 )、低温 ( - 78℃ …     

一类近红外电致发光芴基共聚物的合成和性能研究

基于9,9-二辛基芴与窄带隙单体5,7-二(2-噻吩基)噻[3,4-b]并[1,4]二嗪(DTP),通过Suzuki偶合反应,合成了一系列无规窄带隙的芴基共聚物(PFO-DTP),并对它们的紫外-可见吸收光谱、光致发光和电致发光性能进行了初步研究.共聚物在380 nm和632 nm处有两个明显的吸收峰,其中632 nm处的吸收随着共聚物中窄带隙单体(DTP)含量的增加而加强,最大电致发光峰随着共聚物中窄带隙单体(DTP)含量的增加,从752nm红移到了781 nm.同时与其同分异构体4,7-二(2-噻吩基)苯并噻二唑(DBT)与芴的共聚物PFO-DBT相比,该类聚合物的吸收红移,与近地太阳光谱更为匹配.     

Electropolymerization of 9,9-difluorofluorene in BF3-OEt2 toward a photostable n-type material

Electropolymerization of 9,9-difluorofluorene was successfully carried out in boron trifluoride-ethylether complex (BF₃-OEt₂, BFEE). The obtained polymer, poly(9,9-difluorofluorene) (PFF) showed a good n-type character by cyclic voltammetric analysis owing to the existence of an electronegative difluoromethylene bridge. In addition, PFF exhibited better photostability than its hydrogenated analogue, poly(fluorene) (PF), in photoluminescence measurement.     

Electrochemical tuning of the optoelectronic properties of a fluorene-based conjugated polymer

The electrochemical reduction of a fluorene-based conjugated polymer, poly(9-fluorenone-alt-9,9-dioctylfluorene), was investigated for the first time. The carbonyl group in the fluorenone unit was selectively and quantitatively converted to the methylene group, as determined by (1)H NMR, IR, and energy-dispersive X-ray (EDX) analysis. The optical and electrochemical properties of the polymers were studied by UV-vis, photoluminescence (PL), and cyclic voltammetry (CV) measurements and were found to be tunable by varying the reduction level.     

Vertically-oriented conjugated polymer arrays in mesoporous alumina via simple drop-casting and appearance of anisotropic photoluminescence

Vertically aligned fluorescent polymer arrays with poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) are prepared by simple drop-casting onto mesoporous alumina film. The obtained PFO arrays exhibit anisotropic photoluminescence (PL) along the orientation of the main chains.     

Modification of poly(styrene-alt-maleic anhydride) with 1,3,4-oxadiazole units for electroluminescent devices

New copolymers of poly(styrene-alt-maleic anhydride) (PSMA) modified with 2-(4-aminophenyl)-5-(biphenyl-4-yl)-1,3,4-oxadiazole and hexylamine were prepared. The copolymers, characterized by UV-vis and FT IR spectroscopy, reached 1.22 mol % of the oxadiazole units relative to anhydride groups at the maximum (PSMA-4). Electric and optical properties of the copolymers were studied. The currents obtained depend strongly on the content of oxadiazole units in the copolymers. Currents measured in PSMA-4 were more than two orders of magnitude higher than those measured in the copolymers without oxadiazole. Using polymer blends made of poly(9,9-dihexadecylfluorene-2,7-diyl) and PSMA-4, blue light-emitting devices were fabricated and their photoluminescence and electroluminescence spectra were measured.     

Efficient deep-blue light-emitting polyfluorenes based on 9,9-dimethyl-9H-thioxanthene 10,10-dioxide isomers

We have designed and synthesized a series of deep-blue light-emitting polyfluorenes, PF-27SOs and PF-36SOs, by introducing electron-deficient 9,9-dimethyl-9H-thioxanthene 10,10-dioxide isomers (27SO and 36SO) into the poly(9,9-dioctylfluorene) (PFO) backbone. Compared with PFO, the resulting polymers exhibit an equivalent thermal decomposition temperature (>415 °C), an enhanced glass transition temperature (>99 °C), a decreased lowest unoccupied molecular orbital energy level (E_LUMO) below −2.32 eV, a blue-shifted photoluminescence spectra in solid film with a maximum emission at ~422 nm, and a shoulder peak at ~445 nm. The resulting polymers also show blue-shifted and narrowed electroluminescence spectra with deep-blue Commission Internationale de L'Eclairage (CIE) coordinates of (0.16, 0.07) for PF-27SO20 and (0.16, 0.06) for PF-36SO30, compared with (0.17, 0.13) for PFO. Moreover, simple device based on PF-36SO30 achieves a superior device performance with a maximum external quantum efficiency (EQE_max = 3.62%) compared with PFO (EQE_max = 0.47%). The results show that nonconjugated 9,9-dimethyl-9H-thioxanthene 10,10-dioxide isomers can effectively perturb the conjugation length of polymers, significantly weaken the charge-transfer effect in donor–acceptor systems, substantially improve electroluminescence device efficiency, and achieve deep-blue light emission.     

Liquid crystalline organic semiconductors: nematic spiro[cyclopentyl-1,9′]fluorenes

A number of nematic spiro[cyclopentyl-1,9′]fluorene reactive mesogens with polymerisable oxetane or non-conjugated diene end-groups have been successfully synthesised. The melting and clearing points of these new spiro[cyclopentyl-1,9′]fluorenes are much higher than those of the corresponding 9,9-diethyl- or 9,9-dipropyl-substituted fluorenes, which are present in many light-emitting polymers currently used in polymer light-emitting diodes. The significant difference in transition temperature may be attributed to the lower intermolecular separation induced by the more rigid and less bulky cyclopentyl group, confirmed by molecular modelling. The presence of either these short but flexible aliphatic chains, or a rigid alicyclic group of similar size and shape, results in only small differences in the photoluminescence spectra and efficiency of these model liquid crystalline organic semiconductors, and in their improved thermal stability.     

含噻吩单元的硅芴共聚物的合成及其蓝色电致发光性能

将少量(摩尔分数为1%—3％)含噻吩的窄带隙单体和宽带隙硅芴单体进行共聚, 合成了聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-甲基苯撑-4-基)-噻吩]}和聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-苯撑-4-基)-噻吩]}两类硅芴共聚物, 通过紫外-可见吸收光谱、光致发光光谱, 并制作聚合物发光二极管器件测试电致发光光谱等手段, 系统表征了两类硅芴共聚物材料的性能. 实验结果表明, 噻吩的加入形成了新的蓝色发光中心, 并且实现了从硅芴链段到含噻吩发光中心的有效能量转移. 通过增加发光中心结构的空间位阻来减小其共轭程度, 可以使聚合物的PL和EL光谱发生较大蓝移. 最终得到了效率为0.46%和色坐标(CIE)为(0.19, 0.16)的蓝光LED器件.     

对位取代酚钾与10′10′-二烃基-9,9′-联二吖啶盐电荷转移光谱的研究

10,10′-二烃基-9, 9′-联二吖啶盐有很强的荧光, 在光学材料^[1]和重金属离子的分析^[2]中有重要的应用价值。