9-(2'-硝基苯基)咔唑的电化学聚合及其表征

在含0.1 mol/L四氟化硼四丁基胺的二氯甲烷溶液中,直接阳极氧化9-(2'-硝基苯基)咔唑获得了高质量聚(9-(2'-硝基苯基)咔唑)膜.UV-Vis、FT-IR证明聚合物共轭长链的形成;FT-IR和量化计算确定单体在3,6位聚合;荧光光谱表明聚合物是一种蓝色荧光物质;热重分析表明硝基取代提高了聚咔唑的热稳定性.     

含咔唑基的双光子引发剂光聚合制备微器件

设计并合成了一种带咔唑基的二苯乙烯类双光子引发剂4,4′-双(9-咔唑基-反式-苯乙烯基)联苯(BCSBP),对其单光子和双光子光谱性质进行了研究。在800nm的飞秒激光光源作用下,BCSBP的双光子吸收截面高达483GM。利用BCSBP作为双光子引发剂诱导多官能度单体季戊四醇三丙烯酸酯进行光聚合,得到了亚微米级空间分辨率的聚合物线条,并制备了三维聚合物微器件。     

吖啶橙受溶液pH和浓度变化的光谱研究

利用荧光光谱分析仪研究吖啶橙受溶液pH和浓度变化的吸收光谱和荧光光谱的变化。实验表明,当改变吖啶橙溶液pH和浓度时,它的吸收光谱和荧光光谱发生位移。吖啶橙为1×10-6mol/L时,不同pH的吖啶橙溶液均在(490±3)nm出现一个强吸收峰,pH=6.5,吸收光谱的λm ax=430 nm,发生蓝移;而荧光光谱的λm ax随pH增大发生红移,荧光强度减弱。在浓吖啶橙溶液中,不同pH的吖啶橙溶液的吸收光谱的形状基本相同,出现两个吸收峰,λm ax1分别为(455±3)nm和(430±3)nm,λm ax2分别为(505±4)nm和(510±2)nm,吸收光谱红移;荧光光谱的λm ax均为(535±2)nm,荧光强度荧光很弱。pH相同或相近时,吖啶橙溶液的吸收光谱蓝移和荧光光谱红移,浓度越大,荧光强度越弱。还探讨了吖啶橙在水溶液中的赋存状态,结果表明,在稀溶液中,吖啶橙主要以单体的形式存在;在高浓度吖啶橙溶液中则以吖啶橙单体、二聚体,甚至多聚体形式存在。这说明溶液pH主要影响到吖啶橙分子基态的质子化和氢键的形成能力,使得分子的基态与激发态之间的能量间隔发生了变化,吖啶橙被质子化,则引起发光光谱向短波方向移动,而离解作用,则引起发光光谱向长波方向移动;吖啶橙浓度变化影响吖啶橙在水溶液赋存状态,引起吸收光谱向短波方向移动或向长波方向移动。     

双氰基二苯代乙烯型双光子荧光温度敏感探针

对二甲苯分别经过亲电取代、亲核取代、α-位溴代和亲核取代消除反应得到1,4-二氰基-2-甲基-5-(二乙基磷酰基甲基)苯(Ⅴ);咔唑经过亲核取代反应得到中间体4-(9-咔唑基)-苯甲醛(Ⅶ);中间体Ⅴ与Ⅶ经维蒂希-霍纳尔反应得到目标化合物2,5-二氰基-4-甲基-4′-(9-咔唑基)二苯乙烯(供体-π-受体,D-π-A)(SP),反应总产率达45.5%。SP的溶剂生色范围由412 nm(环己烷)红移至541 nm(二甲基亚砜)(最大发射波长),SP具有非常大的双光子吸收截面(δ_TPA=6930 GM)和高的荧光量子产率[Φ=0.992(环己烷)],其荧光强度对溶剂极性和温度显示很强的依赖性。在单光子荧光发射(OPE)和双光子荧光发射(TPE)谱图中,SP的单、双光子荧光发射强度与温度之间的线性相关系数(R²)均>0.998,表达式分别为I_F=–0.0141θ+1.2881(OPE)和I_F=–0.0143θ+1.2698(TPE)[I_F为荧光强度,θ为温度(℃)]。     

一种共轭炔基咔唑染料分子的合成及光谱性质研究

以二苯硫醚和咔唑为原料,合成了一种以碳碳三键作为桥接基团的新共轭炔基咔唑分子4,4'-二((N-乙基咔唑-3)-乙炔基)苯基硫醚(CZ-S-CZ),其结构经IR、~1HNMR和~(13)CNMR进行表征。通过紫外-可见吸收光谱研究表明,该物质在300~400 nm有较强的吸收。单光子荧光发射光谱研究表明,该化合物的单光子荧光最大发射波长是382 nm,荧光量子产率达到0.4。双光子激发荧光光谱研究表明,CZ-S-CZ在750~780 nm间具有双光子吸收性能,其双光子吸收截面最大可以达267.2 GM。     

含吡嗪、喹啉荧光探针的合成及其对金属离子的识别研究

设计合成了3个含有吡嗪基团的荧光探针分子和喹啉基团的荧光探针分子,其结构通过红外(FT-IR)、质谱(MS)、核磁共振氢谱(1HNMR)进行表征,通过吸收光谱和荧光光谱研究了不同金属离子对目标探针分子的影响。结果表明:Cd2+使401 nm处荧光蓝移了20 nm;Co2+、Hg2+、Pb2+、Zn2+使357 nm处荧光分别红移了20、50、1401、40 nm;Cd2+、Hg2+使349 nm处荧光分别红移了707、5 nm。     

掺杂聚乙烯基咔唑的螺噁嗪光致变色的性能

将PVK(聚乙烯基咔唑)以不同的比例掺杂至螺噁嗪光致变色化合物的体系中,通过对螺噁嗪开环体紫外-可见光谱和聚乙基咔唑荧光光谱的分析可以得出,掺杂体系中聚乙烯基咔唑中的电子空穴可容纳螺噁嗪光致变色过程中迁移的电子,从而提高了螺噁嗪开环的效率。     

3,6-二-(3-(对氯苯)丙烯酰)-9-乙基咔唑的合成及光谱研究

以咔唑为原料,首先与乙酸酐进行酰基化反应得到3,6-二乙酰基咔唑,再通过与溴乙烷反应制得9-乙基-3,6-二乙酰基咔唑,然后与对氯苯甲醛进行缩合反应制得3,6-二-(3-(对氯苯)丙烯酰)-9-乙基咔唑。利用IR、~1HNMR和~(13)CNMR谱对其结构进行了表征,同时进行了紫外-可见和荧光光谱的测定,表明有较好的发光性能。     

晶体8-羟基喹啉铝的合成及光致和电致发光性能

采用水热合成法,得到8-羟基喹啉铝金属配合物。对8-羟基喹啉铝的单晶进行了X-射线衍射分析,确定了结构;同时对此配合物的UV—VIS-NIR,荧光光谱进行了测定和分析,并且以8-羟基喹啉铝的单晶作为发光材料制成器件对其电致发光性能进行了对比研究。     

二苯基金刚烷改性3,6-咔唑共聚物的合成及性能

咔唑类蓝色发光材料固有的低玻璃化转变温度严重限制了实际应用,为了解决这个问题,本文制备了一种高稳定性聚咔唑蓝光材料。以单体3,6-二溴-9-（2-乙基己基）咔唑和N-（2-乙基己基）-3,6-二（4,4,5,5-四甲基-1,3,2-二氧硼戊烷-2-基）咔唑、1,3-二（4-溴苯基）金刚烷为原料,以四（三苯基膦）钯为催化剂,通过调整单体比例,经Suzuki反应合成了数均分子量约3500~6000的3,6-咔唑-二苯基金刚烷共聚物。差热扫描量热测试结果表明,在加入摩尔分数分别为10%、30%和50%的二苯基金刚烷后,共聚物玻璃化转变温度从3,6-咔唑均聚物的66℃分别显著升高至78℃、93℃、106℃,热重测试的失重5%热分解温度同样随着二苯基金刚烷含量的升高而升高。低含量二苯基金刚烷改性共聚物的荧光量子产率较3,6-咔唑均聚物高,显示了优良的荧光传递特性。且共聚物薄膜态时的最大荧光发射波长均处于蓝光最适波长范围内。研究结果表明：二苯基金刚烷的加入显著改善了咔唑聚合物的热稳定性能,还改善了发光性能,制备的共聚物是一种非常有应用前景的新型蓝光材料。     

Syntheses and properties of electroluminescent polyfluorene-based conjugated polymers, containing oxadiazole and carbazole units as pendants, for LEDs

New polyfluorenes (PF)-based conjugated copolymers, containing oxadiazole and carbazole units as pendants, were prepared as the electroluminescent (EL) layer in light-emitting diodes (LEDs) to show that most of them have higher maximum brightness and EL efficiency as compared to poly(2,7-(9,9-bis(2-ethylhexyl)fluorene)) (PF2/6). The prepared polymers, poly[(9-(6-(N-carbazolyl)-hexyl)-9-hexyl)-fluorene-2,7-diyl]-co-[(9-hexyl-9-(6-(4-(5-phenyl-1,3,4-oxadiazolyl)-phenoxy)-hexyl)-fluorene-2,7-diyl)] (Oxd-PF-co-Cz-PF), were soluble in common organic solvents and used as the EL layer in double layer light-emitting diodes (LEDs) (ITO/PEDOT/polymer/Al). All polymers show photoluminescence around λ_max=430 nm (exciting wavelength, 370 nm) and blue EL around λ_max=426 nm. The current–voltage–luminance (I–V–L) characteristics of the polymers show turn-on voltages of 3.5–5.5 V which are lower than that of PF2/6. The maximum brightness and EL efficiency of the device with the configuration of ITO/PEDOT/polymer/Al were 3000 cd/m² at 10 V and 2.13 cd/A at 10.6 mA/cm², respectively, which are all higher than those of PF2/6.     

Optically active vinyl polymers containing fluorescent groups: 5. Fluorescence properties of poly(9-vinyl carbazole) and optically active polymers containing carbazole units

The optically active homopolymers polyl, polyll, and polylll and copolymers of 9-vinyl carbazole with (?)menthyl vinyl ether all exhibit fluorescence related to that of cationically and free radically prepared poly(9-vinyl carbazole). The fluorescence is interpreted for all polymers as arising from three components: monomeric carbazole emission, high energy excimer emission (termed dimer emission for convenience), and a more usual excimer emission arising from conformationally eclipsed carbazole units. Correlations of fluorescence and fluorescence quenching by maleic anhydride, with chiroptical properties and copolymer compositions, suggest that excimer formation is a consequence of rotational freedom within or between isotactic carbazole sequences in the polymer backbones. The isotactic copolymers of (?)menthyl vinyl ether and 9-vinyl carbazole exhibit a relatively strong excimer fluorescence even though mean sequence lengths of carbazole units are comparatively short.     

苯乙烯马来酸酐共聚物（SMA）化学改性制备荧光聚合物及其荧光性能研究

用自行合成的2－氨基噻唑（1），2－氨基－4－苯基噻唑（2），2－氨基苯并噻唑（3）等荧光小分子化合物，与商品化的苯乙烯马来酸酐共聚物（SMA）中的酸酐基团反应，制成聚苯乙烯马来酰亚胺（SMI），实现了SMA化学改性，在获得荧光聚合物的同时，不仅保持了原SMA的可溶性，成膜性等优点，其热性能也得到了改善，通过示差扫描量热（DSC），凝胶色谱（GPC），红外，紫外及荧光光谱等手段表征了荧光聚合物的玻璃化转变温度，分子量及结构与荧光性能关系。     

Synthesis and properties of polyacetylenes having pendent phenylethynylcarbazolyl groups

Novel acetylene monomers substituted with phenylethynylcarbazolyl groups, 3-[(4-octylphenyl)ethynyl]-9-propargylcarbazole (1), 3,6-bis[(4-octylphenyl)ethynyl]-9-propargylcarbazole (2), 9-(4-ethynylphenyl)-3-[(4-octylphenyl)ethynyl]carbazole (3), and 9-(4-ethynylphenyl)-3,6-bis[(4-octylphenyl)ethynyl]carbazole (4) were synthesized, and polymerized with Rh⁺(nbd)[η⁶-C₆H₅B⁻(C₆H₅)₃] and WCl₆-n-Bu₄Sn catalysts. The corresponding polyacetylenes with number-average molecular weights ranging from 9200 to 94?000 were obtained in 20-98% yields. The IR spectra of the polymers revealed that acetylene polymerization took place at the terminal ethynyl group, while the ethynylene group remained intact. The UV-vis absorption band edge wavelengths of W-based poly(3) and poly(4) were longer than those of the other polymers. W-Based poly(4) emitted fluorescence with the highest quantum yield (41%). Poly(1) exhibited excimer-based fluorescence in dilute solution.     

Dendron-functionalized perylene diimides with carrier-transporting ability for red luminescent materials

This paper presents a series of dendrimers via a convergent synthetic approach with three generations, which contain perylene diimide cores, Fréchet-type poly(aryl ether) dendrons, and carbazole (CZ) or oxadiazole (OXZ) peripheral functional groups. The higher generation dendrimer has an obvious site-isolation or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when it forms a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are also studied by steady-state and time-resolved fluorescence spectra under both direct and indirect excitation. The fluorescence data show that there exist two possible mechanisms, Förster energy transfer (FRET) and photo-induced electron transfer (PET), for dendrimers bearing carbazole units. No enhanced core fluorescence is observed because the energy transfer or light-harvesting potential of peripheral carbazole is counteracted by PET. While for dendrimers bearing oxadiazole units, no PET can take place between OXZ and perylene diimide since both of them are high electron affinity. The FRET and higher light-harvesting ability of oxadiazole without PET interfering result in the distinct enhancement of core emission in higher generation dendrimers. DSC results indicate that the incorporation of Fréchet-type poly(aryl ether) dendrons can improve the amorphous property and increase glass transition temperature (T_g). The preliminary EL results with single-layer architectures demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters with carrier-transporting ability. EL emission has the same recombination zone as PL, indicating that the recombination of excitons in fabricated EL devices is not close to cathode or anode vicinity. It is suggested that the site-isolation effect of dendron wedges is attributed to prevent the core luminorphores from approaching electrodes efficiently.     

Synthesis and Characterization of Carbazole–Fluorene–Silole Copolymers as Efficient Green Light Emitting Diodes

A novel series of soluble polyfluorene–carbazole–silole-containing polymers (PF–Cz–S) were prepared through the Suzuki coupling reaction; and, the chemical structures were characterized by elemental analysis and NMR. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were investigated. The copolymers exhibit main absorption peaks at 359?nm for solutions and 354?nm for films with combined contributions from the carbazole and fluorene units. Compared with the solution PL, complete PL excitation energy transfer from the wide band gap segment to a narrow band gap silole unit was achieved by film PL even at a lower silole content. The optical band gaps for PF–Cz–S are between 2.68 and 2.78?eV and the HOMO levels are ?5.65?eV, which are contributed by 3,6-carbazole and fluorene blocks. Light-emitting devices fabricated from these polymers display a maximum external quantum efficiency of 0.44?% with an indium–tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) (PEDOT)/PF–Cz–S/CsF/Al configuration whereas an ITO/PEDOT/PCz–F–S/1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene (TPBI)/CsF/Al with TPBI hole-blocking layer device configuration boosts the efficiency to 2.43?%. The TPBI hole-blocking layer largely improved the efficiency of exciton formation from which the highly efficient green EL from the silole units could be displayed.     

Synthesis of highly conjugated poly(3,9-carbazolyleneethynylenearylene)s emitting variously colored fluorescence

Novel conjugated polymers P1–P7 containing 3,9-linked carbazole units in the main chain were synthesized by the polycondensation of 3-ethynyl-9-(4-ethynylphenyl)carbazole (EEPCz) and dihaloarenes, and their optical and electrical properties were studied. Polymers with weight-average molecular weights of 4100–48,000 were obtained in 24–92% yields by the Sonogashira coupling polycondensation in tetrahydrofuran (THF)/Et₃N at 30 or 50 °C for 48 h. All the polymers absorbed light around 350 nm. The polymers with electron-accepter units exhibited absorption bands originating from charge transfer. The polymers except the one containing azobenzenes emitted variously colored fluorescence with moderate quantum yields upon excitation at the absorption maxima. P1–P3 were oxidized around 0.6 V, and then reduced around 0.5 V. The conductivity of P3 was 1.1 × 10⁻¹⁴ S/cm at 10³ V/cm.     

Synthesis and characterization of fluorene-carbazole and fluorene-phenothiazine copolymers with carbazole and oxadiazole pendants for organic light emitting diodes

We report the synthesis and characterization of new series of the fluorene based polymers with carbazole and oxadiazole pendants for the generation of the white emission out of the EL device. In the fluorene backbone, hole transporting units such as carbazole or phenothiazine were incorporated to improve the EL brightness and efficiency. The PFCzOxd-co-PCzs and PFCzOxd-co-PPTZs in EL spectra showed maximum peaks at around 430 nm and additional large peaks at around 530 and 500 nm, respectively. In case of PFCzOxd-alt-PCz and PFCzCzPCz-co-PFOxdOxdPCz, the EL spectra of the polymers showed two distinct peaks comprising the maximum at 427 nm, which corresponds to the EL spectra of the conjugated backbone, and additional broad peaks at around 540 and 530 nm, respectively. The CIE coordinates of the devices from PFCzOxd-alt-PCz and PFCzCzPCz-co-PFOxdOxdPCz were (0.28, 0.33) and (0.25, 0.32), respectively, approaching the value of the standard white of National Television System Committee (NTSC) (0.33, 0.33).     

Synthesis and characterization of fluorene-based electroluminescent polymers containing silyl groups

Summary Two types of fluorene-based copolymers, poly(9,9'-di-n-hexyl-2,7-fluorenediyl-ethynylene-alt-9-trimethylsilyl-2,7-fluoreneethynylene[P-1], poly(9,9-di-n-hexyl-2,7-fluorenediylethynylene-alt-9,9'-bis-trimethylsilyl-2,7-fluoreneethynylene[P-2] were synthesized by employing palladium catalyzed polycondensation. Resulting polymers showed a good solubility in various organic solvents such as THF, chloroform, dioxane etc. and could be easily spin-coated onto an ITO glass plate to make a fine thin film. Characterization of these polymers includes FT-IR, UV-vis., ¹H and ¹³C-NMR, was conducted. Thermal properties were also investigated by DSC and TGA as well as molecular weight studies. The present polymers exhibited emission of blue-white color. The photoluminescence (PL) spectrum of the polymers showed two peaks at 490 and 540 nm and it was found that electroluminescence (EL) spectra of the polymer [P-2] was very similar to its PL spectrum. Received: 17 September 2001/ Accepted: 12 October 2001     

Efficient white polymer-light-emitting-diodes based on polyfluorene end-capped with yellowish-green fluorescent dye and blended with a red phosphorescent iridium complex

A novel series of blue and yellowish-green light-emitting single polymers were prepared by end-capping of low contents of 4-bromo-7H-benzo [de]naphtha[2′,3′:4,5]imidazo[2,1-a]isoquinolin-7-one (M1) into polyfluorene. Electroluminescence (EL) spectra of these polymers exhibit blue emission (λ_max = 430/460 nm) from the fluorene segments and yellowish-green emission (λ_max = 510/530 nm) from the M1 units. For the polymer (PFNAP-0.06) with the M1 unit content of 0.06 mol-%, its EL spectrum shows balanced intensities of blue emission and yellowish-green emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.25, 0.34). The maximum brightness of the device prepared from the polymer (PFNAP-0.06) is 6704 cd/m² at 10 V with a structure of indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) [PEDOT:PSS]/PVK/emission layer/Ca/Ag. A new white polymer-light-emitting-diode (WPLED) can be developed from the single polymer (PFNAP-0.06) system blended with a red phosphorescent iridium complex [Bis(2-[2′-benzothienyl)-pyridinato-N,C^3′] iridium (acetylacetonate) (BtpIr)]. We were able to obtain a white-light-emission device by adjusting the molar ratio of BtpIr to PFNAP-0.06 with a structure of indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) [PEDOT:PSS]/PVK/emission layer/Ca/Ag. The brightness in such a device configuration is 4030 cd/m² at 9 V with CIE coordinates of (0.32, 0.34).