0000000000464838
AUTHOR
Stefan Glang
Tristriazolotriazines with π-Conjugated Segments: Star-Shaped Fluorophors and Discotic Liquid Crystals
C3-symmetrical tristriazolotriazines substituted with phenylene rings carrying lateral flexible alkoxy side chains were prepared via condensation/ring transformation of cyanuric chloride and tetrazoles. These star-shaped, planar compounds can form broad thermotropic mesophases. Due to the extensive π-conjugation, these compounds are highly emissive and the octupolar donor-acceptor electronic structure results in non-linear optical properties like solvatochromism. Brønstedt acids provoke halochromism of the absorption and of the fluorescence.
Synthesis, Optical and Electrical Properties of Oligo(phenylenevinylene)s Substituted with Electron-Accepting Sulfonyl Groups
Oligo(phenylenevinylene)s (OPV) composed of five rings and electron donating or withdrawing sulfonyl substituents on the central and lateral rings have been investigated. Two strategies were used for the syntheses of the C2-symmetrical OPVs both include PO-activated olefinations as central steps. Six flexible side chains guarantee good solubility in toluene or dichloromethane. In solution and in films stabilised by polystyrene (60%), the chromophores are strongly fluorescent, with emissions in the violet-blue domain from solutions and in the green to orange region from solid films. The redox potentials, determined by cyclic voltammetry, and the optical properties are strongly depending on t…
Arylethynyl-Substituted Tristriazolotriazines: Synthesis, Optical Properties, and Thermotropic Behavior
The synthesis of C3-symmetrical tristriazolotriazines with conjugated arms and lateral alkoxy side chains was performed by a threefold condensation of cyanuric chloride with tetrazoles. Conjugated π segments include phenyl, tolane, and its phenylethynyl-elongated homologue. Disclike and a dendritic molecule have been obtained, and two compounds with a 3,4,5-tris(octyloxy) substitution form broad thermotropic mesophases. The linear optical properties, solvatochromism of the fluorescence, acidochromism, and the two-photon absorption efficiency of selected compounds are reported.
The Medium-Depending Fluorescence of Quadrupolar Donor-Acceptor-Donor Substituted Distyrylbenzenes with High Two-Photon Absorption Cross-Sections
ABSTRACT1,4-Distyrylbenzenes with terminal dialkylamino groups and a central 2,5-disubstitution with electron-accepting groups were prepared via twofold Horner-olefination. These chromophores with a quadrupolar donor-acceptor-donor substitution and C2-symmetry absorb in the violet to green region of the visible spectrum exhibit large two-photon-absorption cross-sections when irrdiated in the NIR. Whereas a variation of the solvent polarity only slightly alters the absorption spectra, the fluorescence appears to be highly responsive. Besides a positive solvatochromism, the emission is very sensitive towards protonation. Quenching or appearance of new emitting species depends on the substitut…
Proton-Induced Multiple Changes of the Absorption and Fluorescence Spectra of Amino-Aza-Oligo(Phenylenevinylene)s
Fluorescent dyes with a high sensitivity of their optical spectra towards changes of the environment were prepared via aldol condensation or Horner olefinations. The main chromophore is a quadrupolar N-substituted 1,4-distyrylbenzene which allows protonation and complexation at various positions resulting in a series of different and significant changes of the optical spectra. The sensitivity of the absorption and emission spectra on solvent polarity, acid, and cations is reported.
3,5-Dialkoxy Substituted Triphenyl-tristriazolotriazines: Fluorescent Discotic Liquid Crystals
Tristriazolotriazines with a threefold 3,5-dialkoxyphenyl substitution were prepared from the corresponding phenyltetrazoles and cyanuric chloride. These star-shaped compounds are discotic liquid crystals that form broad and stable thermotropic mesophases. The thermal behaviour was studied by DSC and polarizing optical microscopy. An increasing length of the side chains reduces the phase transition temperatures, this effect is more pronounced for the crystalline to mesophase transition than for the clearing temperature. XRD on an oriented sample revealed a hexagonal columnar structure for the mesophase. All TTTs emit a strong fluorescence in the UV-violet region.