有机电致发光器件中几种常用组分的荧光光谱研究

利用荧光光谱对电致发光器件(OLED)中几种常用化学组分的荧光猝灭和光诱导电子转移问题进行了研究．发现两种常用的空穴传输材料NPB和TPD与常用电子传输材料AlQ3在光的帮助下可发生电子转移、根据荧光猝灭的Stern—Volmer作图和用单光子记数法测得的荧光寿命而计算得到的猝灭速度常数和扩散速度常数相对应，明确地表明这里的猝灭具有电子转移特征、并对所得的结果进行了讨论。     

含蒽核心第一代π-共轭不对称树状化合物的光学性质

对含蒽核心的第一代π-共轭不对称树状化合物PD-G1的光学性质研究发现：相对G-OH,共轭长度的增加导致了其在吸光、荧光发射强度与范围的提升,蒽核部分的吸光强度的增加,表明其能量漏斗效应; 荧光猝灭实验表明,能与缺电子化合物硝基苯、富电子化合物对二甲氧基苯形成离子对产生荧光猝灭（猝灭常数分别为144和169 L/mol）,说明能同时作为电子受体与电子供体,且对2,4,6-三硝基甲苯（TNT）显示出良好的猝灭响应性,其猝灭常数能达到约557 L/mol,猝灭效率能达到74%,因此在光捕获、发光及荧光传感材料方面有潜在应用价值。     

蒈烯芳氰敏化光氧化反应的研究——Ⅰ.蒈烯对9,10-二腈基蒽荧光的猝灭特性

本文通过研究在不同溶剂中蒈烯对9,10—二腈基蒽(DCA)荧光猝灭的光物理特性及溶剂极性对猝灭速度的影响,温度效应的测定及其在乙腈中双分子猝灭速率常数κ_q值与计算所得自由能的变化(△G)之间的关系符合 RehmWeller关系,证明了菇烯对DCA荧光的猝灭是一个电子转移的动态猝灭过程。     

N,N′-双-β-萘甲基哌嗪分子内激发态复合物形成的混合溶剂效应

本文测定了N,N′-双-β-萘甲基哌嗪(DMNP)在苯与乙腈混合溶剂中的荧光光谱。在乙腈含量<5(mol·dm~(-3))时,乙腈猝灭DMNP苯溶液的荧光符合Stern-Volmer方程,表明极性溶剂分子乙腈与DMNP分子内激基复合物存在着相互作用。随着乙腈含量的增加,DMNP分子内激基复合物(exci-plex)荧光的猝灭与红移以及分子内激基缔合物(excimer)的逐步形成则仅与体系的极性有关。文中还讨论了DMNP激发态复合物形成的机理。     

靛蓝衍生物的光异构化

合成了六个N,N′-双酰基取代的靛蓝衍生物,研究了这类染料的光致变色的宏观动力学。用不同的波长,可以使反式异构体转化为顺式异构体,或使顺式异构体转化为反式异构体。讨论了异构化反应的机理。     

一种新型二胺类空穴传输材料和NPB的合成及表征

以N-苯基-1-萘胺和对溴碘苯为起始原料,经Buchwald-Hartwing偶联反应合成有机发光二极管空穴传输材料N,N′-二[4-(1-萘基苯基氨基)苯基]-N,N′-二苯基-[1,1′-联苯]-4,4′-二胺(2)。以1-溴化萘(1-溴萘)为初始原料与N,N′-二苯基联苯二胺经Buchwald-Hartwing偶联合成了N,N′-[二(1-萘基)-N,N′-二苯基]-1,1′-联苯基)-4,4′-二胺(NPB)。利用~1HNMR、LC-MS等对产品结构进行表征。通过差示扫描量热仪(DSC)测得化合物2和NPB失重5%的温度分别为510℃和491℃,化合物2的玻璃化转变温度Tg为126℃,化合物2和NPB的升华温度分别为395℃和290℃,并通过UV-Vis紫外吸收光谱、荧光光谱研究了两种传输材料的光学性质。     

系列有机染料对Ru(bpy)_3Cl_2发光淬灭的研究

研究系列有机染料在水溶液中对Ru(bpy)3Cl2的发光淬灭,发现它们对Ru(bpy)3Cl2的发光有显著的猝灭作用。Ru(bpy)3Cl2发光淬灭符合Stern-Vo lmer方程,通过Stern-Vo lmer公式分别计算出了对应染料的猝灭速率常数Kg。研究分析了不同化合物的结构对淬灭速率常数的影响,筛选出对配合物发光高效猝灭的有机染料。     

不对称大环铜(Ⅱ)配合物的合成及其晶体结构

以5-氯水杨醛、N,N′-二甲基乙二胺和多聚甲醛合成N,N′-二甲基-N,N′-二(3-甲酰基-5-氯水杨醛)乙二胺(1),化合物1与乙二胺、醋酸铜、高氯酸铅通过模板反应缩合制备了不对称大环铜(Ⅱ)配合物(2),用元素分析、红外光谱、电喷雾质谱对其进行结构表征,X射线单晶衍射分析配合物2晶体(CCDC:787806)属于三斜晶系,P-1空间群,铜(Ⅱ)离子与大环中两个亚胺氮原子、两个酚羟基的氧原子形成4配位。     

以聚醚链相连的9-氨基吖啶、苯甲酸酯二元体系的合成及分子内光诱导电子转移反应

本文用聚四乙二醇柔性链将９－氨基啶和不同取代基的苯甲酸酯连接起来，合成了一类新型二元分子体系。对各体系中９－氨基啶的电子转移荧光猝灭进行了研究，并根据稳态荧光猝灭计算了体系中的荧光猝灭效率和荧光猝灭速率常数。     

N—乙氧甲酰基—N′—取代芳基硫脲的合成与除草活性

通过乙氧基甲酰氯的异硫氰酸酯化，再与芳胺加成反应合成了8种新的N－乙氧甲酰基－N′－芳基硫脲化合物，其结构经过IR、^1HNMR和元素分析等方法证明，初步除草活性测定结果表明部分化合物对植物生长具有很强的抑制作用。     

香豆素酮类化合物的瞬态研究——Ⅲ.香豆素酮和碘鎓盐间的电子转移

本工作采用激光闪光光解法对香豆素酮类化合物敏化碘鎓盐化合物问题进行了研究。结果表明:碘鎓盐化合物能通过电子转移机理猝灭香豆素酮的激发三重态。工作中还用甲基紫精(PQ~(2+))为模型化物,观察到它也能使香豆素酮的三重态猝灭,同时可看到在位于610nm处的PQ~+生成。这些结果说明,在发生电子转移的反应中香豆素酮是电子给体,按Weller公式的计算结果也表明它们之间可发生电子转移反应。     

Evidence for electron transfer of excited indigo dyes with both electron-acceptors and electron-donors

N,N'-Disubstituted indigo derivatives undergo a very efficient electron transfer reaction in their excited singlet state due to a low reduction potential (ca. ?0.6 V). The rate constant of the reaction is of the same order as that of a diffusion-controlled reaction, when the electron-donating molecules have an oxidation potential lower than 1.0 V.Surprisingly, the same dyes undergo a quenching of their singlet excited state by tetracyanoquinodimethane, a strong electron-accepting molecule. This unusual behaviour has been rationalized on the basis of their voltammetric curves. The effect of this phenomenon on the stability of these dyes is discussed on the basis of a self-quenching process.     

The photochemical behaviour of naphthoylenebenzimidazolone dyes in 1-methyl-2-pyrrolidone

The photochemical behaviour of selected naphthoylenebenzimidazolone dyes is discussed in terms of the photobleaching of the dyes in the presence of electron donors (phenylthioacetic acid, N-phenylglycine, ethyl 4-N,N-dimethylaminobenzoate) as well as an electron acceptor (1-methoxy-4-phenylpyridinium tetrafluoroborate) that are used in photoredox systems for light-induced polymerization. The fluorescence quenching of the dyes in the presence of the electron donors and the electron acceptor was also examined.     

固色剂的研究进展及展望

文章综述了固色剂的固色机理、固色剂的类别、及其发展现状和存在问题。目前,市面上的固色剂多是针对活性染料、直接染料或酸性染料等阴离子型的染料,而对于牛仔布常用的靛蓝类还原染料效果却不明显。根据固色剂发展现状及政策要求认为,固色剂将以水性聚氨酯型为发展方向,同时应当加强研究针对靛蓝类还原染料的新型固色剂。     

电子转移剂调控紫精/聚合物薄膜的光致变色性能

紫精/聚合物薄膜光照后产生紫精自由基阳离子,产生明显的颜色变化,但由于自由基阳离子氧化成二价阳离子缓慢,导致薄膜褪色缓慢,加入电子转移剂可以促进薄膜褪色。本文以电子转移剂和苄基紫精摩尔比为1∶1,制备了多种紫精/聚乙烯吡咯烷酮(PVP)聚合物光致变色薄膜,研究了不同电子转移剂对薄膜的光致变色性能、褪色性能以及光疲劳性能的影响。结果表明:加氯化亚锡(SnCl2)的薄膜同空白样的光疲劳行为类似,含苯醌(BQ)或单壁碳纳米管(SWCNT)的薄膜无法实现循环的光写入/擦除;含氯化铜(CuCl2)或氯化铁(FeCl3)的薄膜,无光疲劳现象,具有信息的循环写入/擦除性能。     

Polymers for dye transfer inhibition in laundry applications

The deposition of dyes onto lightly colored garments, or onto lighter sections of multicolored garments, during laundry results in fabric discoloration. In particular, there is a requirement to restrict indigo dye transfer between garments. Polymers may be added to detergent formulations as dye transfer inhibitors to prevent dye transfer by blocking the deposition of fugitive dyes in aqueous solution. This article reports the generation of a range of dye transfer inhibitors produced by condensation reactions that are effective in preventing the transfer of unbound indigo dye to a variety of fiber types. Key design rules relating to polymer hydrophilicity and pendant polymer functionality were established for the creation of effective dye transfer inhibitors. Remarkably, polymers at concentrations as low as 0.1 mg/ml were found to be effective in inhibiting indigo deposition on a variety of fiber types, offering great promise for their inclusion within laundry detergent formulations as dye transfer inhibitors.     

Electrochemistry and electrochromism of a poly(cyclopentadithiophene) derivative with a viologen pendant

N-Methyl-N′-(6-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-4-ylhexyl)-4,4′-bipyridinium dihexafluorophosphate (CPDT-V²⁺-Me) was synthesized. The monomer was electropolymerized on a glassy carbon or an ITO electrode in a potentiodynamic mode to form the corresponding polymer P(CPDT-V²⁺-Me) on the electrodes. During the electropolymerization, two redox peaks of the viologen (V) moiety increased up to several cycles and then decreased while the redox peak of P(CPDT) moiety still increased. Especially, a new oxidative peak a in the range of ca. −0.4 and 0 V versus Ag/Ag⁺ appeared and increased up to several cycles. Peak a almost disappeared after the redox peaks of the viologen moiety almost disappeared. As a result of cyclic voltammetric study, it was shown that peak a originated from the oxidation of reduced viologen moiety via P(CPDT)-mediated electron transfer mechanism. We also found that the electroactivity of viologen moiety in P(CPDT-V²⁺-Me) decreased significantly when the potential was scanned to the second viologen redox (V⁰/V√⁺). In practical applications, the polymer can be used in the potential range from the first viologen redox to P(CPDT) redox. The polymer turned into highly transparent P(CPDT⁺-V²⁺-Me), blue P(CPDT-V²⁺-Me), dark violet P(CPDT-V√⁺-Me), and violet P(CPDT-V⁰-Me) approximately at 0.8, −0.4, −0.8, and −1.7 V versus Ag/Ag⁺, respectively.     

卤化银乳剂颗粒上不对称菁染料J－聚体荧光的研究

卤化银乳剂颗粒上不对称菁染料Ｊ－聚体荧光的研究齐晓燕，陈次平，周本茂，阎文鹏（中国科学院感光化学研究所，北京１００１０１）关键词光谱增感，染料Ｊ－聚体，荧光，荧光寿命，电子转移光谱增感机理的研究是感光科学中的一个重要课题Ｇｉｌｍａｎ［１］和Ｋｕｈｎ等...     

Intercalating Electron Dyes for TEM Visualization of DNA at the Single-Molecule Level

Staining compounds containing heavy elements (electron dyes) can facilitate the visualization of DNA and related biomolecules by using TEM. However, research into the synthesis and utilization of alternative electron dyes has been limited. Here, we report the synthesis of a novel DNA intercalator molecule, bis-acridine uranyl (BAU). NMR spectroscopy and MS confirmed the validity of the synthetic strategy and gel electrophoresis verified the binding of BAU to DNA. For TEM imaging of DNA, two-dimensional DNA origami nanostructures were used as a robust microscopy test object. By using scanning transmission electron microscopy (STEM) imaging, which is favored over conventional wide-field TEM for improved contrast, and therefore, quantitative image analysis, it is found that the synthesized BAU intercalator can render DNA visible, even at the single-molecule scale. For comparison, other staining compounds with a purported affinity towards DNA, such as dichloroplatinum, cisplatin, osmium tetroxide, and uranyl acetate, have been evaluated. The STEM contrast is discussed in terms of the DNA–dye association constants, number of dye molecules bound per base pair, and the electron-scattering capacity of the metal-containing ligands. These findings pave the way for the future development of electron dyes with specific DNA-binding motifs for high-resolution TEM imaging.     

Mediated electron transfer reactions at electrodes coated with poly(viologen)s

Electron and ion transport processes in microdomains of pendant-type poly(viologen)s were analysed by means of rotating disc voltammetry in aqueous media. Stability of poly(viologen)s on the electrode was improved by introducing long alkyl chains. Penetration or the diffusion of ions and the electron-propagation through the polymer layers were greatly affected by the type of supporting electrolyte and chain length of side alkyl groups. Indeed, almost no penetration of large anionic ions was observed in the case of pendant-type poly(viologen) possessing cetyl groups in a perchlorate supporting electrolyte. The electron-propagation through the polymer layers by the self-exchange reactions among redox-active viologen units seemed also to be slow, as the migration of the counter anion of poly(viologen) was limited inside the cationic domain. Similar behaviour was observed in the case of poly(viologen) coatings with ethyl pendant groups, but the electron-propagation was much slower in comparison with the former case. This difference could be attributed to the nature of cationic domains, since the polycations with long alkyl side chains might form a polymer micelle structure with a segregated hydrophobic domain and cationic channel for the electron-propagation.