α(β)-四苯氧基酞菁锌的合成、表征和电致发光性能

以3(4)-硝基邻苯二腈和苯酚为原料,经过两步反应合成了α(β)-四苯氧基酞菁锌,通过红外光谱、紫外光谱、核磁共振谱、质谱和元素分析表征了其结构,比较研究其光谱性质。 并以旋涂发光层的方法制备了电致发光器件,研究其电致发光性质。 固态酞菁材料的光致发光波长红移到866~930 nm范围内的近红外波段,β-位取代酞菁发光波长红移的程度比α-位取代酞菁大。 2种器件电致发光波长和酞菁固体材料的光致发光波长较接近,分别在880和885 nm处。     

可溶性镍酞菁的光谱特性研究

利用UV-Vis吸收光谱、荧光光谱及半经验ZINDO/S方法,研究了4种可溶性镍酞菁(FPcNi、MePcNi、iBPcNi、iPPcNi)的电子吸收光谱和荧光光谱.研究结果表明:随着取代基的供电子能力增加,酞菁的最大吸收波长(λ_max)和发射波长(λ_em)发生红移,摩尔消光系数变小;随着溶液浓度增大,酞菁聚集体浓度增大,λ_max发生蓝移,但浓度对λ_em影响较小,同时荧光相对强度随浓度增大,出现最大值;随着溶剂配合能力的增加,λ_max、λ_em都发生红移.     

α-含氧取代酞菁的聚集性质研究

以3-硝基邻苯二腈为原料分别与苯酚和甲醇反应合成3-苯氧基邻苯二腈和3-甲氧基邻苯二腈, 这些α-取代的邻苯二腈以二甲氨基乙醇为溶剂, 在有无醋酸锌条件下环合, 分别形成α-四苯氧基锌酞菁、α-四苯氧基无金属酞菁、α-四甲氧基锌酞菁、α-四甲氧基无金属酞菁, 对产物结构进行了表征. 光谱分析结果表明, 此类锌酞菁在氯仿等非配位溶剂中能自发形成J型聚集体, 其Q带出现一个红移吸收带, 经UV-Vis光谱、荧光光谱及MALDI-TOF质谱分析表明, 该聚集体的形成机理为基于酞菁分子间的锌-氧自配位相互作用.     

α-四(烷基苯氧基)酞菁配合物的合成与表征

以邻苯二甲酸酐为原料，经硝化、氨化、亲核取代和金属离子模扳等多步反应合成了两个系列共5个叔丁基取代苯氧基金属酞菁配合物，产物经元素分析，IR表征，测定了目标配合物的紫外可见吸收光谱、荧光光谱及在有机溶剂中的溶解性。结果发现：与无取代金属酞菁配合物相比，Q带最大吸收光谱波长红移；在710nm波激发下，目标配合物在环已烷等有机溶剂中均有荧光发射(最大发射波长在760nm左右)；在二氯甲烷、氯仿、环已烷、Py、苯、甲苯、乙基环已烷、乙基溶纤剂等中溶解性能良好。     

含硫甲基的芴-苯结构化合物的合成、结构和性能

通过双Suzuki偶联反应一步合成了2种含硫甲基的芴-苯结构化合物2,7-二(4-硫甲基苯基)-9,9-二己基-芴(a)和2,7-二(2,6-二甲基-4-硫甲基苯基)-9,9-二己基-芴(b).紫外-可见和荧光光谱以及分子轨道理论计算表明,位阻较小的化合物a具有更好的共轭性能,其最大紫外-可见吸收波长达到351nm,比两端苯基含4个邻位取代基的化合物b红移了38nm;化合物a的最大荧光发射波长达到410nm,为典型的蓝光化合物,比化合物b红移了43nm.化合物a和b都具有较高的荧光量子产率,分别为59%和65%,在光电材料方面具有潜在的应用前景.     

蓝光材料2-叔丁基-9,10-二(9,9-二正丙基芴基)蒽的合成与性能表征

本文设计并合成了一种新型蒽衍生物蓝光材料2-叔丁基-9,10-二(9,9-二正丙基芴基)蒽.化合物中引入的柔性烷基链有效抑制了分子间的相互作用,使该化合物不易结晶,同时提高了化合物在有机溶剂中的溶解度.通过量子力学方法计算发现,化合物具有顺反两种稳定构型,分子的平面性差,能减弱分子间相互作用.化合物在二氯甲烷溶液中的最大荧光发射峰在443 nm,在环己烷溶液中测得荧光量子效率为0.78,固态薄膜的最大发射峰波长相对溶液有少量红移(450 nm).热失重和差热分析结果表明,该化合物具有较高的热稳定性,分解温度和玻璃化转变温度分别为365℃和126℃.     

磺化2,3-萘酞菁锌(Ⅱ)、钴(Ⅱ)的电子吸收光谱和荧光光谱的研究

研究了磺化2，3-萘酞菁锌(Ⅱ)、钴(Ⅱ)在DMF(N，N-二甲基甲酰胺)、DMSO(二甲基亚砜)、乙醇、水等溶剂中的电子吸收光谱和荧光光谱．萘酞菁配合物的Q带与相应的酞菁配合物Q带相比，电子吸收光谱红移80～90nm，荧光光谱红移约100nm，荧光强度也显增加．在金属萘酞菁中引入磺酸基，配合物的电子吸收光谱Q带发生红移，但是影响不大、对于相同中心金属的配合物，改变溶剂的种类对配合物的电子吸收光谱的Q带影响较大．在金属萘酞菁环上引入一个磺酸基时，在相同溶剂中与无取代萘酞菁相比发生荧光光谱Q带红移，荧光强度增大．但在萘酞菁环上继续引入磺酸基时，荧光强度反而减少．磺化萘酞菁钴比磺化萘酞菁锌有较大的荧光强度．不同浓度下的电子吸收光谱和荧光光谱说明金属萘酞菁有集聚倾向、能形成基激缔合物．     

芳杂环推拉型大分子的多光子上转换荧光性质

用Wittig反应和Heck反应制备了2个新的芳杂环推-拉型荧光大分子聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N,N'-二(4-苯乙烯撑)]苯胺(P1)和聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N-乙基-3,6-咔唑乙烯撑](P2). P1和P2的分解温度分别为373和412 ℃, 热稳定性良好. 电化学性能用循环伏安法测定. P1和P2的最高占有分子轨道(HOMO)能级分别为-5.39和-5.81 eV, 最低未占有分子轨道(LUMO)能级分别为-2.81和-3.09 eV. 用飞秒Ti:Sapphire激光器测定了P1和P2的三光子和双光子上转换荧光光谱. 在1250 nm波长激发下, 在四氢呋喃溶液中P1和P2的三光子荧光发射峰分别位于510和491 nm. 在800 nm波长激发下, 在四氢呋喃溶液中P1和P2的双光子荧光发射峰分别位于511和495 nm. 在四氢呋喃溶液中大分子P1和P2单光子荧光发射峰分别位于503 和475 nm, P1和P2的荧光量子产率分别为0.80和0.31. 研究了多光子荧光发射过程的溶剂效应. 结果表明, 溶剂极性增大, P1和P2的多光子荧光发射波长明显红移.     

量子限制效应对多孔硅液相电致发光的影响

着重研究多孔硅在阴极偏压下过硫酸铵溶液中电压调制的电致发光现象 .随阴极偏压的增大 ,电致荧光峰位蓝移 ,荧光强度增大 ,同时发现定电压下 ,发生电致发光随时间的衰减伴随着光谱的红移现象 .通过红外光谱、AFM及电化学等手段对电致发光的电位调制机理及荧光衰减机制进行了研究 ,结果表明电致发光与光致发光具有相同的起源 ,电压选择激发不同粒径的多孔硅 ,而导致了发光峰值能量的电位选择性 .在电致发光过程中 ,强氧化剂向多孔硅注入空穴使其表面氧化导致小粒径的硅晶逐渐被剥落 ,使光谱高能部分首先衰减出现了随时间的电致发光红移现象 .这些结果支持量子限制效应在多孔硅液相电致发光中起着重要作用     

2-(2-苯并咪唑)-6-甲基吡啶锌配合物的合成及发光性质

合成了2-(2-苯并咪唑)-6-甲基吡啶及其锌配合物,通过元素分析、摩尔电导率、红外光谱和紫外光谱对产物进行了表征,并运用荧光光谱对配合物的发光性质进行了研究。结果表明,锌配合物在DMF溶液中的荧光最大发射波长为428nm,在固态下的荧光最大发射波长为448nm,均属于蓝光发射,具有作为蓝色发光材料的潜能。     

四取代羧基酞菁锌与白蛋白共价结合物的制备与光谱性质

通过成酰胺键的方式制备了一系列含羧基酞菁和白蛋白(牛血清白蛋白(BSA),人血清白蛋白(HSA))之间的共价结合物,所涉及到的酞菁分别是α-四(4-羧基苯氧基)酞菁锌(1)和α-四[4-(2-羧基乙基)苯氧基]酞菁锌(3),以及它们相应的β位四取代酞菁锌(化合物2和4).比较了游离酞菁以及它们的白蛋白结合物在磷酸盐缓冲溶液(PBS)中的光谱性质.结果表明,当酞菁被共价固定于白蛋白大分子上之后,展现出比游离酞菁更明显的单体特征吸收,而且结合物中的酞菁光谱特征不受体系pH值变化的影响.羧基在酞菁环上的取代位置,对酞菁与白蛋白结合前后的光谱转变幅度有影响,α位取代比β位取代更有利于光谱的变化.化合物1和3的白蛋白共价结合物在PBS溶液中甚至呈现出单体形式为主的光谱特征,Q带最大吸收波长分别位于697和706nm附近.     

Photoluminescence and laser properties of mesostructured SBA-15 monolith doped with coumarin 151

Large, flawless and transparent silica monoliths were prepared at room temperature by solvent evaporation method and loaded with dye. The composites containing dye molecules were characterized by X-ray diffraction, transmission electron microscopy, Uv–vis and photoluminescence spectra. A red-shift in photoluminescence spectrum was observed from the composite monolith compared with that of laser dye in C₂H₅OH solution. The property of laser narrowing has been shown when the composites are pumped at _p = 355 nm by nitrogen laser.     

Electroluminescence of a bichromophoric molecule with a benzoxyazolylcoumarin and carbazole moiety

The electroluminescent properties of a bichromophoric molecule in which a benzoxyazolylcoumarin and carbazole moiety is combined with 1,2-ethylene linkage, i.e. 3-(2-benzoxyazolyl)-7-[2-(9-carbazolyl)ethoxy]-coumarin (CmCz), were investigated. CmCz exhibits fluorescence of different colors in a solid state and solution. Two types of device were made. One consisted of a vacuum vapor-deposited film of CmCz as an emission layer to utilize fluorescence in the solid state; the second consisted of a spin-cast film doped with CmCz as an emission material to utilize fluorescence in the solution. The device with a vapor-deposited CmCz film between electrodes shows a green emission with a luminance of less than 10⁻² cd/m². The multiple layer device in which the CmCz film was sandwiched between a hole transport layer and electron transport layer showed a green emission whose spectrum is identical to the photoluminescent spectrum in the vapor-deposited CmCz film. A maximum luminance of the multiple layer device is about 5000 cd/m². On the other hand, the devices consisting of a spin-cast film containing a hole transport material, an electron transport material and CmCz showed a blue emission whose spectra are identical to the photoluminescent spectrum of CmCz in chloroform. Luminance of these devices is over 100 cd/m². © 1997 John Wiley & Sons, Ltd.     

Preparation, photo- and electro-luminescent properties of a novel complex of Tb (III) with a tripod ligand

A novel Tb(III) complex TbL (L=tris[2-(2-carboxyphenoxy)ethyl]amine, H3L) was synthesized and characterized by means of elemental analyses, IR spectra, thermal analyses, and molar conductivity measurement. The photoluminescent properties of the complex were investigated. In addition, PVK doping Tb(III) complex was fabricated as the emissive layer by spin-coating and its electroluminescent properties were studied, in which the structure of the device was ITO (indium tin oxide)/PVK (polyvinylcarbazole)/PVK: TbL/PBD (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole)/LiF/Al. It was indicated that pure green and narrow bandwidth emission at 545nm from photoluminescence of TbL complex film and the organic electroluminescent device is the characteristic emission of Tb(III) ion, and the electroluminescence spectrum of the device was very similar to that of the photoluminescence of TbL complex film. The lowest triplet level of the ligand was calculated from the phosphorescence spectrum of GdL in N,N-dimethyl formamide (DMF) dilute solution determined at 77K, and the energy transfer mechanisms in TbL complex were discussed.     

二{2-{2-{9-乙基-6-[2-(8-羟基喹啉-2-基)乙烯基]咔唑-3-基}乙烯}-8-羟基喹啉}锌配合物的合成与荧光光谱特性

合成了新的N-乙基咔唑衍生物: 3,6-二[2-(8-羟基喹啉基)乙烯基]咔唑(4)及其锌配合物(5); 化合物4经质谱、红外光谱、核磁共振氢谱、元素分析表征其结构, 并测定了它的荧光光谱. 结果显示: 化合物4的荧光发射为蓝绿色光(500 nm), 其发射光谱随着溶剂极性的增大荧光光谱向长波方向移动(即发生红移); 同时, 考察了化合物5的荧光性质, 其荧光发光峰值为600 nm, 与2-甲基-8-羟基喹啉锌相比, 发生了明显的红移.     

1,2,5-Triphenylpyrrole Derivatives with Dual Intense Photoluminescence in Both Solution and the Solid State: Solvatochromism and Polymorphic Luminescence Properties

Five organic luminophores, 1,2,5-triphenylpyrrole (TPP) derivatives 3 a – e bearing electron-withdrawing or electron-donating groups, have been synthesized by Pd-catalyzed Suzuki coupling of 1-phenyl-2,5-di(4′-bromophenyl)pyrrole and para-substituted phenylboronic acid derivatives. They possess good thermal stabilities with high decomposition temperatures above 310 °C. Investigation of the photophysical properties of the luminogens 3 a – e indicated that they exhibited dual intense photoluminescence in both solution and the solid state due to their twisted conformations, and their fluorescence quantum yields (Φ_F) were determined as 68.7–94.9 % in THF solution and 19.1–52.0 % in solid powder form. Compounds 3 a – c bearing electron-accepting groups exhibited remarkable solvatochromism with large Stokes shifts, attributable to their D-π-A structure and intramolecular charge-transfer effect. In particular, 3 a , bearing aldehyde groups, displayed an obvious red-shift of the emission band from 445 to 564 nm with increasing solvent polarity. However, no obvious solvatochromic behavior was observed for compounds 3 d , e bearing electron-donating groups. The luminophore 3 a exhibited polymorphic luminescence properties and crystallization-induced emission enhancement.     

Triphenylamine and quinoline-containing polyfluorene for blue light-emitting diodes

A novel blue light-emitting polyfluorene-based copolymer PTHD containing electron-rich triphenylamine and electron-poor phenylquinoline side chains in the C-9 position of fluorene unit is described. By comparison of the solution and thin film photoluminescence (PL) spectra of PTHD, a considerable red-shift of Δλ = 10-15 nm was observed in the thin film PL spectrum. The emission intensity of the shoulder peak appeared in dilute solution was also significantly enhanced in the thin film. In contrast to the reference polymer poly{[9,9-dihexylfluorene]-alt-[9,9-di(2,4-diphenylquinoline)fluorene]}, PTHD exhibits higher HOMO energy level, and higher maximum brightness with the PLED device configuration of ITO/PEDOT:PSS/polymer_70% + PBD_30%/TPBI/LiF/Al.     

四(4,4',4'',4'''-N,N-二氨基)四苯乙烯光致发光与分子的构象效应

利用还原偶联方法合成出新化合物四(4,4',4',4''-N,N-二氨基)四苯乙烯（ TDETE）。通过测定该化合物在溶液、掺杂聚合物中及晶体粉末的稳态-瞬态荧光光 谱、荧光量子产率和辐射衰变速率常数等。讨论了分子的构象效应等因素对TDETE 光致发光行为的影响。在一定浓度下TDETE溶液存在着三个发光带,分别为全扭曲 构象分子（位于345nm附近的发光I带）、半扭曲构象分子（位于430nm附近的发光 II带）和激基缔合物（530发光III带）的辐射衰变所致。在聚合物（PMMA）中,一 方面由于分子单键的自由旋转扭曲受到遏制,表现为II带的辐射衰变速率常数(kf 值)增大、同时非辐射衰变速率常数knf值减小;另一方面,TDETE分子之间相互作 用得到加强而有利一缔合物形成,结果,使发光II带和III带合二为一出现强而宽 的发射峰,荧光量子产率从溶液中的0.055提高到0.855。此外,在PMM介制裁中观 测到TDETE分子聚集体在626nm处的发光带（IV）,数粉末态中聚集体IV带的强度骤 增,峰值波长红移至650nm。     

抗抑郁化合物SIPI5358与环糊精形成的非共价复合物

用电喷雾电离质谱(ESI-MS)和串级质谱(MS/MS),并结合紫外光谱、荧光光谱等方法,研究一种芳烷醇哌嗪类抗抑郁化合物SIPI5358与α-、β-、γ-环糊精(CD)制备得到的非共价复合物.质谱分析结果显示,SIPI5358分子可以和α-CD生成配合比为1∶1的非共价复合物,而与β-、γ-CD生成不同配合比的非共价复合物.串级质谱的结果进一步验证β-CD与SIPI5358非共价复合物的组成.用紫外光谱和荧光光谱实验对液相中非共价复合物的形成进行了辅助研究,结果均再次验证了非共价复合物的生成.荧光光谱实验测得SIPI5358与β-CD反应的生成常数Kf=3.45×103 mol.L-1.