Effects of the Structural Rigidity of Polymethine Dye Molecules on Quenching of Their Photoluminescence by an Electric Field and Charge Photogeneration in Poly(N-epoxypropylcarbazole)

For photoconducting poly(N-epoxypropylcarbazole) films doped with cationic polymethine dyes used as an example, it was found that an increase in dye molecular rigidity increased the photoconductivity of the films in the region of dye absorption, quenching effect of an electric field on photoluminescence, and concentration ratio of photogenerated triplet electron–hole pairs to singlet pairs. The effects were enhanced by an increase in the quantum energy of excitation light. The results are explained by a decrease in the dissipation rate of the electronic excitation energy of dye molecules upon growing their rigidity, which accelerates singlet–triplet intersystem crossing in the photogenerated electron–hole pairs via the spin–lattice relaxation mechanism.     

Structure and Adsorption Properties of Nanocrystalline Silicon

The structure of the particles of nanocrystalline silicon synthesized in argon plasma with added oxygen is studied. An amorphous shell composed of silicon oxide is formed on the surface of silicon nanoparticles. The particles form clusters with a fractal structure. The adsorption of nitrogen on a powder of nanocrystalline silicon at 77 K is studied, and adsorption isotherms obtained for nanocrystalline silicon and nonporous silica adsorbents with identical specific surface areas are compared. The values of surface fractal dimension of powdered nanocrystalline silicon are calculated using the Frenkel-Halsey-Hill equation for multilayer adsorption under the dominant contribution of van der Waals or capillary forces. It is shown that surface fractal dimension is a structure-sensitive parameter characterizing both the morphology of clusters and the structure (roughness) of the surface of particles and their aggregates.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 541–547.Original Russian Text Copyright © 2005 by Tutorskii, Belogorokhov, Ishchenko, Storozhenko.     

Pyrylocyanines. 11. Symmetrical tetraphenyl-substituted pyrylo-2-cyanines

Symmetrical polymethine dyes (monomethylidyne, carbo-, and dicarbocyanines), viz., 4,6-diphenylpyrylium, -thiopyrylium, and -pyridinium derivatives, were synthesized. It follows from a comparison of the absorption spectra of pyrylo-2-cyanines and their heteroanalogs with the spectra of the corresponding 4 isomers that these dyes differ from one another with respect to the positions, intensities, and forms of the bands. The pyrylocarbo- and -dicarbocyanines and their sulfur analogs are more deeply colored than their isomers, while the reverse regularity is observed in the pyridocyanine series. The long-wave bands in the spectra of all of the isomers are accompanied by more intensive transitions to the vibrational sublevels than in the case of the isomers.See [1] for Communication 10.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–902, July, 1980.     

Pyrylocyanines. 14. Unsymmetrical pyrylocyanines based on 2,3-polymethylene-4,6-diphenylpyrylium salts

Unsymmetrical 4,6-diphenylpyrylo-2-carbo- and dicarbocyanines, as well as the analogous pyridocyanines, containing 3-ethylbenzothiazolium and 1,3,3-trimethyl-3H-indolium residues and an ethylene or trimethylene bridging grouping between the position of the polymethine chain and the position of the pyrylium or pyridinium residue were synthesized. The introduction of bridging groups is generally accompanied by a bathochromic effect and intensification (in the pyrylocyanine series) or weakening (in the pyridocyanine series) of the fine structure of the absorption bands. On the basis of the deviations calculated from the centers of the absorption bands and the dependences of the vinylene shifts and the absorption band widths on the structure of the dyes it was concluded that the trimethylene bridging groups in the examined cases increase the electron-donor character of the heterocyclic residues in the dyes more markedly than the ethylene bridging groups.See [1] for Communication 13.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1327–1331, October, 1981.     

Dioxane analogs of flavylium salts

The synthesis of benzodioxane derivatives of 1-benzopyrilium salts is reported and their reaction with nucleophiles is investigated.Taros Shevchenko University, Kiev 252017. Translated from Khimiya Geterotsiklicheskikb Soedinenii, No. 3, pp. 322–324, March, 1995. Original article submitted February 6, 1995.     

Structures of terminal heterocyclic groups and fluorescence-spectral properties of polymethine dyes

The fluorescence and absorption bands of carbocyanines containing pyrylium or benzoxazolium groups, their nitrogen-, sulfur-, and selenium-containing analogs, their benzohomologs, or isomeric analogs of pyrylium as terminal groups were mathematically processed using the method of moments. The regularities in the displacement of the absorption and fluorescence bands following the replacement of the heteroatom and variations of the positions of substituents in the terminal groups were explained using perturbation theory. Based on quantum-chemical calculations, the changes in the bond orders in the ground and excited states of the dyes were studied. The correlations between the moments of the experimental absorption and fluorescence bands and the frequency and the form of the chromophore vibrations were analyzed. The transition from pyrylo-4-cyanines to isomeric pyrylo-2-cyanines leads to substantial broadening of the bands, an increase in the Stokes shifts, decreases in the coefficients of asymmetry, kurtosis, and fine structure of the bands, as well as a decrease in the quantum yield of fluorescence.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2194–2203, September, 1996.     

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.     

Optimization and use of composite coatings based on silicon oxide and polyvinylsulfonic acid for the adsorption-spectrophotometric determination of iron(II) and zinc(II) phenanthrolinates

Conditions are optimized for preparing sol-gel modified composite films based on silicon oxide and polyvinylsulfonic acid in the presence of the Tween 20 nonionic surfactant as a template for the adsorption of Fe(II) and Zn(II) phenanthrolinates. The adsorption of Zn(II), Cu(II), Mn(II), Co(II), and Ni(II) phenanthrolinates followed by their development on the surface with Rose Bengal oxyxanthene dye was studied by spectrophotometry. The variation of the pH of the solution pH and the addition of 0.01 M of EDTA enhanced the selectivity of determining Zn(II) using a film obtained under optimum conditions. The applicability of the proposed thin-film coatings to the adsorption-spectrophotometric determination of Fe(II) and Zn(II) in the ranges of 0.2–5.6 and 0.3–5.0 mg/L, respectively, was shown. The procedure was used to determine zinc in vitamin preparations, a food supplement, and an insulin preparation. The accuracy of determination was checked by atomic absorption spectrometry. The detection limit for zinc was 0.06 mg/L at a liquid phase volume of 25 mL and absorption layer thickness of 0.015 ± 0.003 mm.     

Direct synthesis of nitrogen-containing filamentous carbon on a high-percentage Ni-Cu catalyst

Nitrogen-containing catalytic filamentous carbon (N-CFC) of chemical composition NC₁₈-NC₁₀₄ has been synthesized by the decomposition of pyridine (Py) from gaseous mixtures with argon or H₂ at 550–800°C on Ni/Al₂O₃ (Ni) and Ni-Cu/Al₂O₃ (Ni-Cu) high-percentage catalysts. The activity of the Ni-Cu catalyst in Py decomposition in mixtures with H₂ is about one order of magnitude higher than its activity in Py/Ar mixtures (more than 70 g N-CFC per metal gram in 4.5 h at 750°C), which is interpreted as arising from the nickel-catalyzed hydrogenation of Py. The formation and growth of carbon fibers occurs through the decomposition of Py (from Ar/Py mixtures) and/or Py hydrodenitrification products (from H₂/Py mixtures). The carbon material has been characterized by elemental analysis, low-temperature nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). The effect of the noncatalytic reactions of Py and its transformation products on the composition and texture of N-CFC is discussed.