新型双发色团染料荧光光谱及其寿命的研究

有效的染料激光操作需要较高的荧光量子效率,若丹明是在500~700 nm光谱区中一类最重要的激光染料.然而,染料的基态分子和三线态对辐射能量的吸收将会大大降低激光输出效率,再者,由于若丹明类染料在紫外区的吸收系数较小,为了有效吸收泵浦能量(如用XeCI准分子激光,308 nm),就必须使用高浓度染料溶液,在这种情况下,若丹明类染料较小的Stokes位移就势必造成基态分子更大的重复吸收,即造成更大的谐振腔损耗^[1].     

New Disperse Dyes for Polyester Microfibres

A serics of disperse dyes bearing ether groups have been synthesized.The visible absorption spectra of them were studied.Their fastness on polyester microfibres were investigated .     

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。     

DFT Investigations(Geometry Optimization,UV/Vis,FT-IR,NMR, HOMO-LUMO,FMO, MEP,NBO, Excited States) and the Syntheses of New Pyrimidine Dyes

In the present work, the molecular structures of two new synthesized dyes:(4,6-dimethylpyrimidin-2-ylamino)(5-p-tolylisoxazol-3-yl)methanol(PS-1) and N-(4,6-dimethylpyrimidin-2-yl)-5-phenylisoxazole-3-carboxamide(PS-2), have been investigated using density functional theory(DFT) in dimethylformamide(DMF) for the first time. The electronic spectra of new dyes in a DMF solvent were carried out by time dependent density functional theory(TD-DFT) method. After quantum-chemical calculations two new dyes for the optoelectronic applications were synthesized. FT-IR spectra of the title compounds are recorded and discussed. NucleusIndependent Chemical Shifts(NICS) calculations have also been carried out for the title compounds. The computed absorption spectral data of the title compounds are in good agreement with the experimental data, thus allowing an assignment of the UV spectra. The HOMO and LUMO molecular orbitals, excitation energies and oscillator strengths for the dyes have also been calculated and presented.     

Cyanine dyes from thiazolomorpholinium and thiazolodihydrothiazinium salts

Cyanine dyes have been synthesized from previously unknown thiazolo [3, 2-c]morpholinium and thiazolo[3, 2-c]dihydrothiazinium salts, and their absorption spectra have been determined.     

Effects of Donor and Acceptor on Optoelectronic Performance for Porphyrin Derivatives: Nonlinear Optical Properties and Dye-sensitized Solar Cells

Typical asymmetric donor-π-bridge-acceptor(D-π-A) zinc porphyrin dyes have been synthesized, and further modified by reacting the ethynyl groups of them with click reagent through a formal [2+2] click reaction. The electronic interaction between the push and pull electronic groups and the click reaction process were investigated by UV-Vis absorption spectroscopy. The nonlinear optical(NLO) properties of the dyes were studied by the Z-scan technique and clearly reverse saturable absorption to saturable absorption(RSA-SA) transition could be observed through click reaction of the dyes with TCNE. Furthermore, the photovoltaic properties of these porphyrin dyes were reaso- nably explained by the J-V curve fitting based on the equivalent-circuit model as well as the comparison between the absorption and incident-photon-to-current-conversion efficiency(IPCE) spectra. Besides, these dyes with different donors or acceptors could self-assembly into different microstructures by phase transfer methodology.     

Analogs of styryl dyes and the simplest AZO dyes from 2-dimethylaminothiophene

The condensation of 2-dimethylaminothiophene with the appropriate derivatives of quaternary benzothiazole salts has give the vinylene-homologous series of dyes with the structure (I). By coupling with benzenediazonium salts, the simplest azo dyes of structure (III) have been synthesized. The influence on the absorption spectra of the replacement of a dimethylaniline nucleus in polymethine and azo dyes by a 2-dimethylaminothiophene nucleus has been investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 923–925, July, 1973.     

Synthesis of new hetarylazoindole dyes from some 2-aminothiazole derivatives

A new series of heterocyclic disperse dyes were prepared by diazotization of some 2-aminothiazole derivatives and subsequent coupling with indole compounds. The dyes were characterized by UV-Vis, FT-IR, ¹H NMR, and mass spectra (LC-MS). Solvent effects on their visible absorption spectra were estimated. The color of the dyes is discussed with respect to the substituent therein. The effects of acids and bases on the visible absorption maxima of the dyes are also reported. Replacement of methyl group in the 4-position of the thiazole ring by phenyl group leads to red shift of the absorption maximum due to π-electron-donating properties of the phenyl group, while weak electron-withdrawing chlorine or bromine atom in the para-position of the phenyl group in the 2-amino-4-phenylthiazole fragment induce a small blue shift relative to 2-amino-4-phenylthiazole derivatives. Introduction of an electron-withdrawing 4-nitrophenylsulfonyl group into the thiazole ring produces bathochromic shift of the absorption maximum in all solvents. Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 592–599. The text was submitted by the authors in English.     

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.     

Synthesis,Characterization, and Fluorescence Studies of Novel Heterocyclic Azo Dyes Derived from Benzothiazole

Ten novel fluorescent azo disperse dyes 2a – e (open forms) and 3a – e (closed forms) were obtained by the coupling reaction of carbocyclic amine based diazonium chloride with compounds 2 and 3 . The synthesized dyes were characterized by elemental analysis, high‐resolution mass spectrometry, Fourier transform infrared, and NMR spectral techniques. Moreover, we investigated the substituent effect and solvatochromic properties of the dyes on absorption and fluorescence spectra. At the same time, the absorption and emission spectral data of the closed form dyes 3a – e were compared with the open form dyes 2a – e due to more planarity of the closed form dyes that lead to the extension of the π–electron conjugation.     

The absorption and structure of fluorescein and its ethyl derivatives in various solutions

Ethyl fluorescein and diethyl fluorescein were synthesized. Their absorption spectra in different pH solutions and in organic solvents with different polarity were measured. These were systematically compared with those of fluorescein, and the forms of these dyes in various media were reasonably assigned.     

N-苄基吲哚三碳菁染料的合成及性能

合成了5种N-苄基吲哚三碳菁染料,通过红外光谱、核磁共振氢谱及元素分析确证了其结构,并研究了电子吸收光谱、荧光光谱、光稳定性及溶解度。结果表明,染料溶液和膜的最大吸收波长均为780～830nm;染料在二氯乙烷中的溶解度大于在乙醇中的溶解度;氮原子上苄基的引入极大地改进了染料的光稳定性(与HITCI比较).     

Coloured particles by dispersion polymerization

Coloured particles have been prepared by dispersion copolymerization of colourless vinyl monomers and polymerizable anthraquinone dyes. The dyes were synthesized by condensation of methacryloyl chloride and amino- or hydroxy-substituted anthraquinones. This paper describes the formation by dispersion polymerization of coloured copolymer particles of diameter greater than 5 microns. The coloured particles were characterized by size, visible absorption spectra, and solution properties of the copolymers.     

Synthesis and optical properties of acidochromic amine-substituted benzo[a]phenazines

A new series of alkylamine- or arylamine-substituted benzo[a]phenazines have been synthesized from 1,2-naphthoquinones by employing simple sequential Michael-type addition with a variety of primary and secondary amines and the condensation reaction of the resulting amine-substituted 1,2-naphthoquinones with o-phenylenediamine. They exhibited absorption peaks originating from the charge transfer transition between the amine and pyrazine segments and benzo[a]phenazine localized π-π* transitions. Although the absorption spectra of the dyes were not significantly influenced by the nature of the solvents, addition of TFA led to a prominent red-shift in the absorption spectra owing to the protonation at the quinoxaline segment which enhanced the electron-accepting ability. The qualitative trends observed in the optical properties and acidochromism were supported by density functional theoretical computations. The dyes displayed positive solvatochromism in the emission spectra suggestive of a more polar excited state. The dyes were also characterized by a quasi-reversible reduction couple originating from the pyrazine segment which underwent shifts corresponding to electron-donating strength of the amine segment.     

含有萘酰亚胺的菁染料太阳能电池敏化剂的合成

通过Click反应把萘酰亚胺化合物连接到含有醛基的吲哚上,再通过醛基和吲哚碘盐的Knoevenagel缩合反应合成出带有萘酰亚胺部分的菁染料,用NMR、MS、元素分析、UV-Vis等方法对其结构和性能进行了表征和测试。     

Synthesis and properties of functional dyes with squaraine–naphthalene diimide hybrid structure

Naphthalene diimides (NDIs) are promising candidate for electron acceptors due to their low-lying HOMOs and LUMOs. The functinalization of soluble NDIs at the 2,6-position affects the absorption and electrochemical properties. In this study, NDI-based hybrid dyes NDI-SQ-A, B fused with squaraine chromophore were designed and synthesized in order to elucidate the effects of the substitution on their optical and electrochemical properties. These dyes were successfully synthesized by Stille coupling reactions using 3-stannylcyclobutenediones and brominated NDI derivative, followed by a condensation reaction. DFT calculation predicts that the present dyes adopt distorted structures coming from a steric hindrance between semisquaraine and NDI moieties. The hybrid dyes show low-lying LUMOs due to the introduction of electron-deficient NDI moiety and broad absorption spectra in the far-red region. The absorption spectra of their thin films were bathochromically shifted relative to those in solution, indicating that hybrid dyes formed J aggregates.     

Synthesis and spectral properties of non-symmetrical red and near IR emitter dibenzoBODIPYs

New symmetrical and non-symmetrical benzoBODIPYs have been synthesized from diketones. For the two series the 3 and 5 positions have been substituted by different aromatic rings and onto benzo sub-units different groups have been introduced. The methodology of diketones self-condensation provides symmetrical dyes. By cross-condensation reaction, these positions can be differentiated and specific functions connected to the desired positions. These molecules have been fully characterized and their optical properties analyzed by both experimental and theoretical means. They are red to NIR emitters with a range of emission from 679 to 780?nm in CH₂Cl₂. They show maxima of absorption between 651?nm and 732?nm, strong ε of around 100,000?M^?1?cm^?1 and quite good quantum yields from 16% to 75%. The thienyl moiety on α-positions of the nitrogens generates the highest red shifts. Meanwhile dimethylamino groups in the same positions bring, besides chemical properties, proton sensitive dyes. The bromine atom onto the dibenzo sub-units exhibits good reactivity through Sonogashira coupling reactions. This approach provides multifunctional red to NIR dyes with endless possibilities of combination of chemical properties.     

Ultrafast Photoinduced Electron Transfer in Viologen‐Linked BODIPY Dyes

New boron‐dipyrromethene (BODIPY) dyes linked to viologen are prepared and their photophysical and electrochemical properties are investigated. Both synthesized molecules have similar electronic absorption spectra with the absorption maximum localized at 517 and 501 nm for dye 1 and dye 2 , respectively. They exhibit well‐defined redox behavior, highlighting the presence of BODIPY and viologen subunits, with little perturbation of the redox potential of both subunits with respect to the parent compounds. Both dyes are heavily quenched by photoinduced electron transfer from the BODIPY to the viologen subunit. The transient absorption technique demonstrates that dye 2 forms the viologen radical within a timeframe of 7.1 ps, and that the charge‐separated species has a lifetime of 59 ps. Sustained irradiation of dye 2 in the presence of a tertiary amine allows for the accumulation of BODIPY–methyl‐4,4′‐bipyridinium (BODIPY–MV⁺), as observed by its characteristic absorption at 396 and 603 nm. However, dye 2 does not generate catalytic amounts of hydrogen under standard conditions.     

Protolytic Properties of Thiofluorescein and Its Derivatives

Ionization constants of thiofluorescein, 4-nitro-, 4,5-dinitro-, 2,4,5,7-tetrabromo-, and 2,4,5,7-tetraiodothiofluoresceins, and also of 4,5-dibromofluorescein and N-ethyl-4,5-dinitroazafluorescein in 50 wt % aqueous ethanol have been determined. The electronic absorption spectra of their ionic and molecular forms have been recorded and analyzed. The behavior of these dyes can be described in terms of the scheme of prototropic equilibria proposed previously for fluorescein and its halo derivatives.     

Synthesis of Novel Azo Dyes Containing the Thiophene Moiety

A series of disperse dyes have been synthesized by diazotation of 2-aminothiophene derivative and coupling with various N-arylmaleimides. The dyes were characterized by IR spectral studies, visible absorption spectra, and elemental analysis. The dyeing performance of these dyes was assessed on nylon fabric. These dyes were found to give yellowish brown to reddish violet shades on dyeing with very good depth, levelness, and brightness on fabric. The percentage dyebath exhaustion and fixation on fabric was found to be very good. The dyed fabric showed poor light fastness and good to excellent fastness to washing, rubbing, perspiration, and sublimation.