The synthesis and structural, thermal, optical and theoretical characterization of new tris[1,2,4]triazolo[1,3,5]triazines were performed to support their application as liquid crystals and advanced materials.
Discotic molecules comprising a rigid aromatic core and flexible side chains have been promisingly applied in OLEDs as self-organizing organic semiconductors. Due to their potentially high charge carrier mobility along the columns, device performance can be readily improved by proper alignment of columns throughout the bulk. In the present work, the charge mobility was increased by 5 orders of magnitude due to homeotropic columnar ordering induced by the boundary interfaces during thermal annealing in the mesophase. State-of-the-art diodes were fabricated using spin-coated films whose homeotropic alignment with formation of hexagonal germs was observed by polarizing optical microscopy. The photophysical properties showed drastic changes at the mesophase-isotropic transition, which is supported by the gain of order observed by X-ray diffraction. The electrical properties were investigated by modeling the current-voltage characteristics by a space-charge-limited current transport with a field dependent mobility.
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.
The electrical responses of a columnar liquid crystal (a diimidodiester derivative of benzo[ghi]perylene) deposited either by spin-coating or by thermal evaporation into a typical OLED device are compared. For the spin-coated film, homeotropic alignment was induced by thermal annealing, which enhanced the charge carrier mobility significantly. For the evaporated films, homeotropic alignment could not be obtained by annealing. However, a degree of rectification higher than 3 orders of magnitude was achieved, even without annealing, with an electrical response similar to the response of the aligned spin-coated film. A trap-limited space-charge-limited current model was used to extract the charge carrier mobility directly from the current-voltage curves. Grazing incidence wide-angle X-ray scattering confirmed the homeotropic alignment of the annealed spin-coated film, whereas the columns are mostly oriented parallel to the surface in the evaporated case. In a field-effect transistor with bottom-gate bottom-contact geometry, the evaporated film exhibited a typical behavior of an n-type transistor. The degree of intermolecular order is thereby strongly dependent on the deposition method where vacuum deposition leads to a higher order. This higher order, however, impedes reorientation by annealing of the evaporated film but leads to improved charge transport between the electrodes even without homeotropic alignment of columnar liquid crystal.
The dehydrating cyclotrimerization of 1‐tetralone in the presence of titanium tetrachloride at high temperatures leads to homotruxene, a nonplanar arene in which the twist angles between its three outer benzene rings and the central benzene are stabilized by ethylene bridges. This non‐planar configuration allows for pronounced spin–orbit coupling and a high triplet energy, leading to room‐temperature phosphorescence in air with a lifetime of 0.38 s and a quantum yield of 5.6 %, clearly visible to the human eye after switching off the excitation. Triplet–triplet annihilation is found to simultaneously lead to a substantial delayed fluorescence, unprecedented from a pure hydrocarbon at ambient conditions, with a lifetime of 0.11 s.
Al 3+ -Mg 2+ mixed oxides were prepared by coprecipitation and characterized with scanning electron microscopy (SEM), energy dispersive Xray fluorescence (EDXRF), temperature programmed desorption of CO 2 (CO 2 -TPD), and N 2 adsorption/desorption isotherms (BET and BJH methods). By increasing the MgO concentration up to 31.8% (w/w), X-ray diffraction (XRD) measurements suggested an incipient magnesium aluminate spinel (MgAl 2 O 4 ) phase. However, the spinel crystalline structure was obtained only after calcination at 950 °C. These materials were tested as catalysts in the propanolysis reaction of methyl paraoxon. This reaction in the presence of the more efficient incipient MgAl 2 O 4 spinel is of the order of 2.5 × 10 5 -fold faster than the spontaneous propanolysis reaction and results in the formation of a product that is structurally related to a family of flame retardants. The different products of propanolysis and hydrolysis were identified by electrospray ionization mass spectrometry (ESI(+)-MS), ESI(+)-MS/MS) and liquid chromatography mass spectrometry (LC-MS/MS).
g Nanoenabled drug delivery systems against tuberculosis (TB) are thought to control pathogen replication by targeting antibiotics to infected tissues and phagocytes. However, whether nanoparticle (NP)-based carriers directly interact with Mycobacterium tuberculosis and how such drug delivery systems induce intracellular bacterial killing by macrophages is not defined. In the present study, we demonstrated that a highly hydrophobic citral-derived isoniazid analogue, termed JVA, significantly increases nanoencapsulation and inhibits M. tuberculosis growth by enhancing intracellular drug bioavailability. Importantly, confocal and atomic force microscopy analyses revealed that JVA-NPs associate with both intracellular M. tuberculosis and cell-free bacteria, indicating that NPs directly interact with the bacterium. Taken together, these data reveal a nanotechnology-based strategy that promotes antibiotic targeting into replicating extra-and intracellular mycobacteria, which could actively enhance chemotherapy during active TB.
In the present work, we show the synthesis and full characterization of 12 new 1,3,4-oxadiazole nonsymmetrical star-shaped molecules containing amide or imine connecting groups, variable number and positions of linear or branched alkoxy chains and different sizes of the aromatic core. Thermal and liquid crystalline properties were investigated by POM, DSC, TGA and XRD scattering, while photophysical studies (UV-vis absorption, emission and quantum yield) were realized in solution and in solid state (film). Most compounds form enantiotropic hexagonal columnar phases while all molecules show blue luminescence. The variations in thermal and photophysical properties were correlated with different structural parameters showed by each molecule.
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