Protonation and Alkylation of Cross-conjugated Ketones Containing a Terminal N-Methylpyrrole Ring

The protonation and alkylation of cross-conjugated ketones containing a terminal N-methylpyrrole ring takes place at the oxygen atom. Protonation is accompanied by a strong bathochromic shift of the absorption maximum in the electron spectrum, while alkylation leads to ethoxypolymethine salts. The possibility of using these salts for the synthesis of ethoxycyanine dyes was studied.     

氯取代硫三碳菁染料的合成及性能

本文合成了七个硫三碳菁.其中四个具有桥环的菁染料。测定了它们的电子吸收光谱,讨论了结构对光稳定性的影响。并发现镍络合物能有效地抑制菁染料的光退色。     

三碳菁染料的研究

三碳菁染料的吸收在近红外区,可用作卤化银感光材料的红外增感染料,近年来在红外激光染料和光信息记录介质等方面也得到了开发及应用。在多甲川链上引入桥环可提高染料的稳定性。本文合成了9种含芳胺基取代的桥链三碳菁,讨论染料结构与其增感性能关系。     

桥链七甲川菁的合成及光性能

菁是一种具有多功能用途的染料,除用作卤化银感光材料及有机光导材料的光谱增感剂、光记录材料中记录介质外,还可作为染料激光器中用的激光染料.我们曾合成了四甲川苯乙烯菁、五甲川(艹粦)及五甲川吡喃鎓等红外染料作为激光染料,测定了它们的光性能.本文合成了具有桥链的七甲川菁,研究了这些桥链七甲川菁的吸收光谱及荧光光谱,并以YAG激光倍频(532nm)作泵浦源,测定了它们的激光调谐范围、中心波长及激光转换效率.     

含吲哚核端基多甲川菁染料的合成及性能

我们曾合成了具有桥环的硫三碳菁及多甲川苯乙烯菁,并测定了光学性能。本文报道吲哚环为端基的桥链三碳菁和四甲川苯乙烯菁的合成及在有机溶剂中电子吸收光谱及溶解性能的测定。所用仪器同前,7种多甲川菁染料的合成反应如下:     

冠醚菁染料及其中间体的特征红外光谱

本文首次报道冠醚菁染料3,3’-二乙基-5,6,5’,6’-双骈-(15-冠-5)-硫碳菁碘盐(1)和3,3’-二乙甲基-5,6-骈-(15-冠-5)-硫碳菁碘盐(2)以及合成中间体:4’-溴5’-硝基-苯骈-15-冠-5(3),2.2’-二硝基-4,5,4’,5’-双骈-(15-冠-5)-二本基二硫化物(4),2-甲基-5,6-骈-(15-冠-5)-苯骈噻唑(5)和2-甲基-3-乙基-5,6-骈-(15-冠-5)-苯骄噻唑碘盐(6)的特征红外光谱图。     

The length of the polymethine chain and the spectral-luminescent properties of symmetrical cyanine dyes

The general characteristics that relate the length of the polymethine chain of symmetrical cyanine dyes to their spectral-luminescent properties depending on the electron-donor character of the heterocycles and the nature of the solvent are formulated. For various types of symmetrical cyanines, the Stokes shifts decrease with the elongation of the polymethine chain due to weakening of the vibronic interactions. The vinylene shifts of the band maxima are essentially constant and fall within the range 100 to 130 nm depending on the nature of the heterocycles and the solvent. When the polymethine chain elongates the fluorescence quantum yields first increase and then decrease. The greater the effective length of the heterocycle the stronger the decrease. The fluorescence decay occurring when the polymethine chain gets longer is associated with intensification of the internal conversion. For symmetrical cyanines, the changes in the shapes of the electronic bands (their width, asymmetry, excess, and fine structure) as the chain elongates are governed by the competing effects of the vibronic and intermolecular interactions. The former decrease as the chain lengthens, causing the narrowing of the absorption bands for the lower vinylogs. On the other hand, the latter increase as chain lengthens, which leads to broadening of the bands for the higher vinylogs. The higher the solvent nucleophilicity and the greater the deviation of the electron-donor ability of the heterocycle from the average value the greater the broadening. Any elongation of the polymethine chain of symmetrical cyanines causes only narrowing of the bands and an increase in the asymmetry, excess, and structuring in the fluorescence spectra, which, unlike the absorption spectra, is independent of the electron-donor character of the heterocycles and the nature of the solvent. These effects are caused by the fact that, in contrast to absorption, changes in the shape of emission bands with increasing chain length are governed predominantly by vibronic rather than by intermolecular interactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1227–1239, July, 1994.     

Singlet oxygen generation ability of squarylium cyanine dyes

The quantum yields for singlet oxygen generation of several squarylium cyanine dyes derived from benzothiazole, benzoselenazole and quinoline, displaying absorption within the so-called “phototherapeutic window” (600–1000 nm), were determined, envisioning their potential usefulness for photodynamic therapy (PDT). The determination was performed by a direct method measuring the luminescence decay of the dyes in the near infrared. Considering the absorption and the quantum yields displayed by some of the dyes, these seemed to be potential candidates as sensitizers for PDT.     

Cyanine Dyes Containing Quinoline Moieties: History,Synthesis, Optical Properties,and Applications

Cyanine dyes carrying quinoline moieties are an important class of organic molecules that are of great interest for applications in many fields like medicine, pharmacology, and engineering. Despite their exceptional properties, such as stability, high molar extinction coefficients, and high pH-sensitivity, this class of dyes has been less analyzed and reviewed in the last few decades. Therefore, this review article focuses on discussing the history of quinoline compounds, various synthetic routes to prepare quinolinium salts and symmetrical and asymmetrical mono-, di-, tri-, penta- and heptamethine cyanine dyes, containing quinoline moieties, together with their optical properties and applications as photosensitizers in photodynamic therapy, probes in biomolecules for labeling of nucleic acids, as well as imaging agents.     

NIR Light-Induced ATRP for Synthesis of Block Copolymers Comprising UV-Absorbing Moieties

NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [Cu^II/(TPMA)]Br₂ (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol.