No abstract

No abstract

No abstract

No abstract

Sol–gel glass matrices in which organic laser dyes are embedded can be used as the gain medium in solid‐state, continuously tunable lasers. Such lasers are very simple to construct, and potentially very compact and efficient. Unlike the commonly used liquid dye laser systems, solid‐state dye lasers can be made mechanically robust and portable. In this article, the development of sol–gel/dye lasers, including the sol–gel technology, dye properties, and laser operation, is reviewed. In addition, new solid‐state hosts (such as polyurethane/silica ORMOSILs), additional organic dyes (cyanines), and new studies on the stability of the dyes are presented. Copyright © 2004 John Wiley & Sons, Ltd.

A vinylogous series of highly dipolar merocyanines were designed to study their solvatochromism in a wide range of solvents including low-polarity alkanes. It has been revealed that the lower vinylogues indeed have negative solvatochromism in the full range of solvent polarities starting from n-hexane, while the hexamethinemerocyanine exhibits reversed solvatochromism. With the extreme ranges of solvatochromism, the studied dyes possess 5-7 times weaker solvatofluorochromism, which can be rationalized via their decreased dipolarity in the fluorescent state. They also demonstrate an inverse dependence of their fluorescence quantum yield on solvent polarity and have near-record Stokes shifts in high-polarity media. The experimental data are supplemented by the results of DFT quantum chemical analysis of dye electronic structures in both the ground and excited states with PCM solvent field simulation.

Absorption and fluorescence spectrum band moments (center of gravity, width, asymmetry, excess, and fine structure) have been determined in a wide range of solvents with different polarities for inverse solvatochromic di-, tetra-, and hexamethinemerocyanines derived from 1,3-diphenyl-2,3-dihydro-1H-benzimidazole. Juxtaposition of the quantum-chemically calculated (by the semiempirical AM1 method) charges, bond orders, and dipole moments of the merocyanine molecules in the ground and excited singlet states with the experimentally observed spectral fluorescent characteristics suggests that the molecular electronic structure in the two states can vary from a nonpolar polyene via a polymethine to a charge-separated polyene, depending on the length of the polymethine chain and the medium polarity. As shown, solvatofluorochromism gives rise to smaller spectral band shifts than those of solvatochromism. This effect is attributable to weaker intermolecular solute-solvent interactions in the fluorescent excited state due to the more equalized charges as compared to those of the ground state. A lack of mirror symmetry of the absorption and fluorescence spectra has been revealed for di- and tetramethinemerocyanines (broadened fluorescence bands) as well as for hexamethinemerocyanines (narrowed fluorescence bands); the two cases are accounted for by the different behavior of vibronic and intermolecular interactions in the course of absorption and emission. As found for merocyanines, the electronic structure of their fluorescent state approaches the cyanine limit and the ground state becomes increasingly polyene-like with lengthening of the polymethine chain. A close vicinity of the excited state to the cyanine limit causes a dramatic increase in fluorescence quantum yields and a decrease in Stokes shifts observed for higher merocyanine vinylogues.

A associação do corante catiônico indoeptametinocianina com vários corantes aniônicos (quatro sulfonaftaleínas e cinco xantinas) em solução aquosa foi investigada usando espectroscopia de absorção no visível. Os valores das constantes de associação estão na faixa de 10 4 a 7 × 10 7 mol -1 L. Em todos os casos, um efeito hipocrômico significativo foi observado para a banda de absorção do cátion (λ max = 737 nm). O mesmo foi observado para a interação do cátion indotrimetínio (λ max = 540 nm) com espécies aniônicas. Interações eletrostáticas, de Van der Waals e hidrofóbicas são identificadas como as forças que dirigem esta associação. A adição de surfatantes iônicos destrói os compostos de associação do corante, primeiramente devido à interação com os íons de corante com carga oposta. Este processo é acompanhado pela restauração dos espectros de absorção visível dos corantes aniônico e catiônico.The association of the cationic dye indoheptamethine cyanine with various anionic dyes (four sulfonephthaleins and five xanthenes) in aqueous solutions was detected using the Vis-spectroscopic method. The values of the association constants are within the range (10 4 to 7×10 7 mol -1 L). In all the cases a substantial hypochromic effect is observed for the Vis absorption band of the cation (λ max = 737 nm). The interaction of indotrimethinium cation (λ max = 540 nm) with anionic species manifests itself in analogous manner. Electrostatic, Van der Waals, and hydrophobic interactions are regarded as driving forces of the association. Addition of ionic surfactants destroys the dye associates, primarily due to interactions with the oppositely charged dye ions. This process is accompanied by the restoration of the initial Vis absorption bands of both the cationic and the anionic dye.