基于2，3-萘-18-冠-6单元的共轭高分子对金属离子的荧光传感器

能发射蓝绿色荧光的共轭高分子由单体1,4-二溴-2,3-萘-18-冠-6(M-2)与1,4-二乙烯基-2,5-二丁氧基苯(M-3)通过Pd催化的Heck偶联反应合成制得。通过荧光和紫外-可见光谱探讨了高分子对金属离子的响应性质,其中Hg²⁺能使高分子荧光淬灭、吸收增强,但As^Ⅲ、Pb²⁺和K⁺对高分子的荧光光谱改变很小。结果表明以2,3-萘-18-冠-6作为荧光团和识别位点的共轭高分子可作为有效识别Hg²⁺的荧光化学传感器。     

1,3,5-三芳基-2-吡唑啉化合物光物理行为的研究

合成了一组带不同取代基的三芳基吡唑啉化合物,对它们在不同极性溶剂中的光物理行为(如荧光量子产率,荧光寿命等)进行了测定指出:这类化合物在光的激发下除存在有分子内共轭条件下的电荷转移行为外,还存在着分子内非共轭条件下的电子转移,本工作还以三芳基吡唑啉化合物为猝灭剂对氧鎓盐的荧光猝灭能力进行了研究,并对所得结果作了讨论。     

基于1,1'-联-2-萘酚衍生物的手性荧光传感器

具有光活性的1,1′-联-2-萘酚（BINOL）衍生物是近年来研究较多的C2轴不对称芳香化合物,不仅具有很强的手性诱导作用,而且在适合结构基团修饰下能产生很强的荧光,可作为一类有效而灵敏的荧光化学传感器。在与手性胺、氨基醇、氨基酸、α-羟基羧酸、手性醇和单糖等手性有机化合物作用时,该荧光化学传感器在不同识别位点接受客体分子、通过光诱导电子转移（PET）及电子交换能量转移（EET）等引起共轭高分子内能级发生变化,使得所有这些相互作用十分灵敏地在其发光强度和能量上反映出来,具体表现在化学传感器荧光增强与减弱或发射波长的变化上。本文总结了近年来1,1′-联-2-萘酚衍生物的荧光化学传感器在手性异构体识别领域的最新研究进展。     

1-萘基-琥珀酰亚胺的合成与结构性能研究

本文报道用α-萘胺和琥珀酸酐合成1-萘基-琥珀酰亚胺(NPr),并用FT-IR、DSC、X-射线衍射和荧光等方法研究了该化合物的结构与性能.DSC和X-射线衍射结果表明,纯净NPr的熔点与John L. Hubbard报道结果(147~149℃)不同,应为(158.3±0.2℃);熔融淬火样品仍存在部分结晶,并且在一定温度下发生冷结晶;FT-IR结果表明羰基伸缩振动产生反对称振动(1705 cm^-1)和对称振动(1779 cm^-1)的能级分裂;荧光光谱结果则进-步表明该化合物的电子云排布结构与单体萘环相似, 其原因可归于羰基的诱导效应和共轭效应对氮原子的影响.     

含吡啶端基9,10-双芳基蒽共轭分子的合成、聚集诱导荧光增强及双光子诱导荧光

通过Heck反应合成了2个以吡啶为端基的9,10-双芳基蒽共轭分子9,10-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(4Py-PAA)和9,10-二{4-{4-[N,N-二(2-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(2Py-PAA),化合物结构经过1H NMR,13C NMR,HRMS-MALDI-TOF确证.测定了化合物在不同极性溶剂中的紫外吸收光谱、荧光光谱、荧光寿命及量子产率,测算了4Py-PAA和2Py-PAA的偶极矩.通过循环伏安法研究了它们的前线轨道能级.测定了4Py-PAA和2Py-PAA的固体荧光光谱、固体荧光量子产率及在不同含水量的水/THF混合溶液中的荧光光谱.实验发现4Py-PAA在THF溶液中发出蓝绿色荧光,固体时发出红色荧光,在含水量为70%的水/THF混合溶剂中发出黄色荧光,荧光强度是纯四氢呋喃(THF)的3倍,呈现聚集荧光增强性质.在800 nm飞秒激光下采用双光子诱导荧光参比法测定了4Py-PAA和2Py-PAA在THF溶液中的双光子吸收截面分别为193和101 GM.实验结果表明含有2位和4位吡啶端基9,10-双芳基蒽共轭分子具有良好的荧光发射性能及双光子吸收性质.     

己基取代的1,4-二(2-噻吩基)苯并[c]哒嗪合成与光谱性质研究

本文设计并合成了一系列含氮原子的缺电子芳香片段,包括以苯并哒嗪作为核心、以富电子噻吩衍生物作为共轭延长链的有机共轭小分子1,4-二(2-噻吩基)苯并[c]哒嗪(5a)、1,4-二[2-(3-己基噻吩基)]苯并[c]哒嗪(5b)和1,4-二[2-(5-己基噻吩基)]苯并[c]哒嗪(5c).通过紫外光谱和荧光光谱研究,证明在共轭体系中的不同位置引入烷基链,可以有效影响化合物的能隙,调节化合物的光电性质.     

2[(N-乙基)-1-吩噻嗪基]腙的合成及聚集荧光增强性能

以氮-氮单键连接2个吩噻嗪环构成共轭结构, 合成了2[(N-乙基)-1-吩噻嗪基]腙, 并对其进行了结构表征. 该化合物在四氢呋喃溶剂中呈分散态时无荧光; 在四氢呋喃/水混合溶剂中呈现聚集荧光增强. 荧光增强是由于聚集态中分子内单键旋转受分子堆积效应的阻碍, 氮-氮单键连接的2个吩噻嗪环趋于平面化以及J-聚集体形成的协同作用使非辐射跃迁减少所致. 同时, 利用这种聚集荧光增强性质考察了该化合物对血红蛋白的探针识别性能.     

2-芳基苯并噁唑衍生物与光物理行为研究

对2-芳基苯并噁唑衍生物的光谱及光物理行为进行了研究。结果表明,该系列化合物与常见分子内共轭电荷转移化合物的特性明显不同。分析了存在差异的原因,指出该类化合物的较强的荧光发射能力与其分子中的C=N双键的异构化受阻密切相关。     

8-羟基喹啉-5-磺酸金属络合物的荧光特性及其应用研究

本文报道了8-羟基喹啉-5-磺酸的金属络合物在不同条件下的荧光特性,探讨了使用激光-时间分辨技术,建立镁、铝荧光分析方法的可能性.     

1-(2-苯并噻唑基)-5-(2-苯基-1,2,3-三唑基)-3-芳基-2-吡唑啉衍生物的合成及其荧光性能

以2-苯基-1,2,3-三唑基-4-甲醛为原料,与苯乙酮或取代苯乙酮发生羟醛缩合生成相应的查尔酮；再与2-肼基苯并噻唑反应,合成了5个含1,2,3-三唑基、苯并噻唑基的新型吡唑啉衍生物，其结构经¹H NMR、 IR和元素分析表征。荧光性能研究结果表明：该类化合物具有良好的荧光性,其最大发射波长在427～444 nm,荧光强度大小与衍生物中不同的取代基有关     

Photoinduced intramolecular charge transfer and S2 fluorescence in thiophene-pi-conjugated donor-acceptor systems: experimental and TDDFT studies

Experimental and theoretical methods were used to study newly synthesized thiophene-pi-conjugated donor-acceptor compounds, which were found to exhibit efficient intramolecular charge-transfer emission in polar solvents with relatively large Stokes shifts and strong solvatochromism. To gain insight into the solvatochromic behavior of these compounds, the dependence of the spectra on solvent polarity was studied on the basis of Lippert-Mataga models. We found that intramolecular charge transfer in these donor-acceptor systems is significantly dependent on the electron-withdrawing substituents at the thienyl 2-position. The dependence of the absorption and emission spectra of these compounds in methanol on the concentration of trifluoroacetic acid was used to confirm intramolecular charge-transfer emission. Moreover, the calculated absorption and emission energies, which are in accordance with the experimental values, suggested that fluorescence can be emitted from different geometric conformations. In addition, a novel S(2) fluorescence phenomenon for some of these compounds was also be observed. The fluorescence excitation spectra were used to confirm the S(2) fluorescence. We demonstrate that S(2) fluorescence can be explained by the calculated energy gap between the S(2) and S(1) states of these molecules. Furthermore, nonlinear optical behavior of the thiophene-pi-conjugated compound with diethylcyanomethylphosphonate substituents was predicted in theory.     

Photoinduced Electron and Energy Transfer in Dyads of Porphyrin Dimer and Perylene Tetracarboxylic Diimide

Two compounds containing a porphyrin dimer and a perylene tetracarboxylic diimide (PDI) linked by phenyl ( 1 ) or ethylene groups ( 2 ) are prepared. The photophysical properties of these two compounds are investigated by steady state electronic absorption and fluorescence spectra and lifetime measurements. The ground state absorption spectra reveal intense interactions between the porphyrin units within the porphyrin dimer, but no interactions between the porphyirn dimer and PDI. The fluorescence spectra suggest efficient energy transfer from PDI to porphyrin accompanied by less efficient electron transfer from porphyrin to PDI. The energy transfer is not affected by the dimeric structure of porphyrin or the linkage between the porphyrin dimer and PDI. However, the electron transfer from porphyrin to PDI is significantly affected by either the linkage between the donor and the acceptor or the polarity of the solvents. The dimeric structure of the porphyrin units in these compounds significantly promotes electron transfer in nonpolar, but not in polar solvents.     

Beiträge zur Chemie der Pyrrolpigmente, 84. Mitt.: Darstellung und Lumineszenz bichromophorer 5-Aryl-dipyrrinderivate

Summary 1,3- and 1,4-Bis-dipyrrin-benzenes and their various zinc and difluoroboryl chelates are prepared. Their absorption and fluorescence spectra are compared with those of the corresponding mono-dipyrrin derivatives. The conformations of these compounds are analyzed using the ring current model and absorption spectra. Dipole-dipole type transfer of excitation energy is discussed to represent a main photophysical channel in these compounds.

     

具有荧光发射能力有机化合物的光物理和光化学问题研究

有机化合物的结构、构象和环境效应对发光化合物的荧光发射具有重要的影响.本文从化合物激发态的衰变过程出发,侧重于过程的光化学与光物理问题对发光行为和机制进行讨论.如:化合物分子结构的受阻和桥键化对发光的影响;光激发下的光诱导电子和电荷转移及其相互转化;化合物扭曲的分子内电荷转移(TICT);溶剂分子和发光化合物分子间不同的相互作用及对发光的影响;在发光过程中存在着最佳的发光构象等.对于这些问题的研究和掌握,将有利于设计和合成具有高荧光量子产率的发光化合物,更好地解释在研究中出现的种种现象和在实际工作中应用它们.文章还引用了大量发光化合物作为实例,对工作中所得的结果进行了详细讨论.     

Fluorescence resonance energy transfer between polyphenolic compounds and riboflavin indicates a possible accessory photoreceptor function for some polyphenolic compounds

The photoreceptive extreme tip of the wheat coleoptile exhibits intense green-yellow fluorescence under UV light, suggesting the presence of UV-absorbing materials. Fluorescence spectra of the intact coleoptile tip and tip homogenate showed the presence of the known photoreceptor pigments flavin and carotene, and a preponderance of phenolic compounds. Absorption spectra and fluorescence spectra of various phenolic compounds showed close overlap with the absorption and fluorescence spectra of the wheat coleoptile tip homogenate. Fluorescence spectra of several phenolic compounds showed close overlap with the absorption bands of flavin, carotene and pterine, suggesting possible energy transduction from phenols to these photoreceptors. Excitation of gentisic acid and ferulic acid with 340 nm light in the presence of flavin showed enhancement of flavin fluorescence in a concentration- and viscosity-dependent fashion, indicating fluorescence resonance energy transfer between them and riboflavin. Furthermore, several phenolic compounds tested generated superoxide anion on excitation at 340 nm, suggesting that superoxide-dependent signal cascades could operate in a polyphenol-mediated pathway. Phenolic compounds thus may act as accessory photoreceptors bringing about excitation energy transfer to the reactive photoreceptor molecules, or they may take over the function of the normal photoreceptor in genetic mutations lacking the system, or both processes may occur. The responses of plants to UV-B and UV-A light in mutants may be explained in terms of various phenolics acting as energy transducers in photoreceptor functioning.     

Two Dehydroabietic Acid-based Arylamines: Synthesis, Crystal Structure and Fluorescent Properties

Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.     

双(三氯甲基)三嗪类化合物光生酸反应的研究

对 3种具不同结构 (三氯甲基 )三嗪化合物的光致生酸及光敏化生酸问题进行了研究 .从其吸收光谱、荧光光谱、荧光猝灭以及光致生酸过程的测定结果表明 ,三嗪化合物的敏化光致生酸具有电子转移性质 .发现在三嗪化合物分子中存在着归属于核的局域发光以及分子内的电荷转移发光两个部分 .局域的激发与发光和化合物光致生酸有着密切的关系 ,而电荷转移发光则会增强或扩充化合物的吸收和发射光谱范围 ,在光致生酸中也有重要的作用 .一种完美的光致生酸化合物分子的设计和合成必须对上述两个方面均加以注意 ,使能达到互补和协同的作用     

用荧光光谱法研究OLED用的新型蓝色发光染料和三-（8-羟基喹啉）铝(AlQ_3)的光诱导电子转移和激基复合物的生成

在合成了三种新型发射蓝光化合物的基础上，对它们在溶液中的光物理行为作 了详细研究。发现它们的荧光能强烈地被三-（8-羟基喹啉）铝所猝灭，并在荧光 光谱的长谱部分出现因发生光诱导电子转移而生成激基复合物的发光。几个方面的 工作-如猝灭常数的测定，电子转移过程自由能的计算，都表明化合物荧光猝灭过 程的电子转移性质。此外，还讨论了因出现光诱导电子转移和激基复合物给OLED器 件带来的影响，特别对三种作为器件发射蓝光化合物的优劣进行了讨论，表明化合 物DPF有着最佳的发光特征。     

Chemically induced dynamic electron spin polarization-detected energy transfer. Substrate size effects and solvent dependence

Time-resolved electron paramagnetic resonance spectroscopy is used to probe energy transfer from aromatic photoexcited triplet states to azo compounds in liquid solution. The observation of chemically induced dynamic electron spin polarization in the spectra gives precise information regarding the spin physics and mechanism of the energy transfer process. The substrate size is varied by altering the chain length of alkyl chains covalently attached to the azo compounds via ester or amide linkages. The solvent dependence of the energy transfer process is also investigated. The results are discussed in terms of Dexter and F?rster mechanisms for energy transfer, the properties of the excited states, and the diffusive properties of the molecules in the solvents of interest. Decomposition rate studies and fluorescence measurements are also reported.