Columnar Liquid Crystalline Glasses by Combining Configurational Flexibility with Moderate Deviation from Planarity: Extended Triaryltriazines.

Triply phenanthryl- and tetrahelicenyl-substituted triazine-hexaalkyl esters with short alkyl chains show glass transitions conveniently above room temperature within the hexagonal columnar liquid crystalline state, resulting in a solid columnar order at room temperature. As the hexagonal columnar mesophase is easily aligned with the director perpendicular to a solid substrate, such glassy columnar liquid matrices are aimed at for the orientation of guest emitters, to obtain anisotropic emission. A condition for face-on alignment on substrates are attainable melting and clearing temperatures, which is achieved with the moderately nonplanar tetrahelicenyl derivatives in spite of their short alkyl periphery. An unusual phase transition between two columnar mesophases of same hexagonal symmetry, but very different long-distance regularity of the column lattice, is found in one phenanthryl homolog.

Dissymmetric Triaryltriazines: Small Mass Columnar Glasses.

Columnar liquid crystals with very small molecular masses that form anisotropic glasses well above room temperature are obtained by mixed dissymmetric substitution of sym-triazine with ester-bearing phenyl and phenanthryl or tetrahelicenyl moieties. The combination of low molecular symmetry with configurational flexibility and short polar ester moieties stabilizes the mesophase over large temperature ranges and induces pronounced calorimetric glass transitions within the anisotropic fluid despite the smallness of the molecules. In contrast to more symmetrical homologs, no ester tails longer than ethyl are necessary to induce the liquid crystalline state, allowing for the near-absence of any insulating and weight-increasing alkyl periphery. Films drop-cast from solution show in all cases emission spectra that do not show significant change of fluorescence emission upon annealing, indicating that the columnar hexagonal mesoscopic order is obtained directly upon deposition from solution and is resistant to crystallization upon annealing.

Nematic Triphenyltriazine Triesters and the Induction of the Columnar Mesophase by Fluorine Substitution.

Whereas their para homologs are not mesogenic, the disk-shaped triphenyltriazine meta-trialkylesters obtained via trimerization of 3-cyanobenzoic alkylester, which are configurationally more flexible, exhibit a monotropic nematic mesophase. Introduction of fluorine atoms into the alkyl chains or into the phenyl moieties leads to the appearance of an enantiotropic columnar mesophase. If fluorine is introduced both in the chains and in the phenyl moieties, only a monotropic mesophase remains. Fluorination of either the alkyl chains or the aromatic core, but not both, appears thus as a simple means of inducing or stabilizing columnar self-assembly in disk-shaped systems. As the homeotropically alignable columnar mesophase can thus be made to persist at room temperature, as energies higher than 3 eV of the first excited triplet state are computed in agreement with the value reported for the parent arene, and as they are not fluorescent themselves, these compounds are of promise as aligning host matrices for blue-emitting TADF devices with improved light outcoupling. Dilution of a columnar with a nonmesogenic homolog induces the nematic state, indicating that the nanoscopic make-up of both mesophases is closely related.

Catalytic chalcogenylation under greener conditions: a solvent-free sulfur- and seleno-functionalization of olefins via I2/DMSO oxidant system.

Herein, we report a solvent- and metal-free methodology for the alkoxy-chalcogenylation of styrenes, using molecular iodine as a catalyst, DMSO as a stoichiometric oxidant, and different nucleophiles under microwave irradiation. This eco-friendly approach afforded the desired products in good to excellent yields in only 10 min. In addition, using the same protocol, we carried out the cyclization reaction of relevant molecules, such as lapachol derivatives.

Emission ellipsometry used to probe aggregation of the luminescent 2,1,3-benzothiadiazole dyes and ordering in an E7 liquid crystal matrix.

The incorporation of dyes in liquid crystal matrices has been exploited to produce enhanced displays, but it can also be used to probe ordering in liquid crystals and to assess intermolecular interactions and dye aggregation. In this study, we investigated polarized absorption and emission of the luminescent dyes 4,7-bis(2-(4-(decyloxy)phenyl)ethynyl)-[2,1,3]-benzothiadiazole (1A) and 4,7-bis{2-[4-(4-decylpiperazin-1-yl)phenyl]ethynyl}-[2,1,3]-benzothiadiazole (5A) in the E7® liquid crystal. The electronic structures of both 1A and 5A dyes were affected by the matrix and by the analysis of the line shape of emission we could determine that the dyes form J aggregates. This achievement is significant because obtaining this type of information for small molecules requires ordered matrices, which is difficult to obtain for these dyes. Using emission ellipsometry we were able to determine the ordering of the E7 molecules, but this was possible only with the larger 5A dye. The smaller 1A was not entirely ordered in the E7 matrix and this calls for caution in other types of work where dopants are used as probes to infer the properties of the matrix. The emission ellipsometry data for the dyes allowed us to detect the enhanced birefringence in the matrix, thus confirming the theoretical prediction.

Luminescent columnar liquid crystals based on tristriazolotriazine.

Five discotic molecules comprising a tris[1,2,4]triazolo[1,3,5] triazine core were designed and synthesized to obtain luminescent and charge-transporting columnar liquid crystalline materials. With the exception of one compound containing terminal hydroxyl groups all compounds presented a wide thermal range and stable columnar liquid crystalline phase, characterized by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction (XRD) techniques. The phase formation appeared to be associated to some extent with interdigitation of the alkoxy and benzylalkoxy portion, as suggested by the XRD results. All compounds have a strong blue luminescence in solution and solid phase. At the temperature at which the compounds enter in the mesophase the luminescence decreases significantly. This result suggests that entrance into the Col(h) phase is accompanied by a better π-stacking of the peripheral phenyl rings compared to the solid phase, consistent with the intramolecular distances (3.5 Å) observed in the XRD analysis. These compounds based on tristriazolotriazine are quite robust with good optical and thermal properties for application as solid state emitters, and we anticipate that they may provide an interesting alternative to other discotic molecules based on N-heterocycles, which generally present a high-temperature Col(h) phase.

Synthesis of 2,1,3-Benzoxadiazole Derivatives as New Fluorophores-Combined Experimental, Optical, Electro, and Theoretical Study.

Herein, we report the synthesis and characterization of fluorophores containing a 2,1,3-benzoxadiazole unit associated with a π-conjugated system (D-π-A-π-D). These new fluorophores in solution exhibited an absorption maximum at around ~419 nm (visible region), as expected for electronic transitions of the π-π* type (ε ~2.7 × 107 L mol-1 cm-1), and strong solvent-dependent fluorescence emission (ΦFL ~0.5) located in the bluish-green region. The Stokes' shift of these compounds is ca. 3,779 cm-1, which was attributed to an intramolecular charge transfer (ICT) state. In CHCl3 solution, the compounds exhibited longer and shorter lifetimes, which was attributed to the emission of monomeric and aggregated molecules, respectively. Density functional theory was used to model the electronic structure of the compounds 9a-d in their excited and ground electronic states. The simulated emission spectra are consistent with the experimental results, with different solvents leading to a shift in the emission peak and the attribution of a π-π* state with the characteristics of a charge transfer excitation. The thermal properties were analyzed by thermogravimetric analysis, and a high maximum degradation rate occurred at around 300°C. Electrochemical studies were also performed in order to determine the band gaps of the molecules. The electrochemical band gaps (2.48-2.70 eV) showed strong correlations with the optical band gaps (2.64-2.67 eV).

Hybrid compounds with two redox centres: modular synthesis of chalcogen-containing lapachones and studies on their antitumor activity.

Chalcogen-containing ß-lapachone derivatives were synthesized using a straightforward methodology and evaluated against several cancer cell lines (leukaemia, human colon carcinoma, prostate, human metastatic prostate, ovarian, central nervous system and breast), showing, in some cases, IC50 values below 1 µM. The cytotoxic potential of the lapachones evaluated was also assayed using non-tumor cells: human peripheral blood mononuclear cells, two murine fibroblast lines (L929 and V79 cells) and MDCK (canine kidney epithelial cells). These compounds could provide promising new lead derivatives for anticancer drug development. This manuscript reports important findings since few authors have described C-3 substituted ß-lapachone with potent antitumor activity. The methodology employed allowed the preparation of the compounds from lapachol within a few minutes in a green approach.