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Two neutral copper(I) halide complexes ([Cu(BTU)2X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N′-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI–MS, elemental analysis, IR, and NMR spectroscopies (1H and 13C), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH...X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 × 10−7 S·cm−1 was achieved at 430 K for the chloro-complex and 1.37 × 10−6 S·cm−1 at 440K for the related bromo-complex. [ABSTRACT FROM AUTHOR]

• Polymer Dispersed Liquid Crystal (PDLC) systems using chitosan biopolymer matrix and the nematic liquid crystal (LC) mixture E7 were obtained. • The N-Iso phase transitions have shifted in the heating DSC scan to lower temperature values for PDLC samples with approximately 2.7 °C. • Dielectric loss and electrical conductivity spectra along with their temperature variation have been analyzed. • Havriliak-Negami function was used for obtaining the characteristic time and the activation energy. Polymer Dispersed Liquid Crystals (PDLC) systems were obtained using chitosan as a biopolymer matrix and the nematic liquid crystal (LC) mixture E7 in various concentrations (30, 40 and 50% E7 in chitosan). Several techniques were used to analyze the obtained films: polarizing optical microscopy (POM), IR spectroscopy (FTIR), differential scanning calorimetry (DSC) and dielectric spectroscopy (DS). FTIR spectroscopy revealed minor changes for all PDLC films, suggesting weak interactions between LC and chitosan matrix. For each sample a clear segregation of the nematic droplets could be observed by POM. DSC measurements show that the phase transitions have shifted to lower temperature values for PDLC samples with approximately 2.7 °C compare to pure E7. The values of α (fraction of LC in the droplets) for compositions of 30, 40 and 50 wt% E7 in Chitosan were 0.48, 0.55 and 0.61 respectively, that are lower than for E7/PMMA system. The qualitative and quantitative analysis of the permittivity spectra obtained by DS reveals the fact that there are no significant changes in the molecular dynamics attributed to pure LC E7 compared to the PDLC composites, leading to the conclusion of the existence of a weak interaction between the two components, fact confirmed by the findings from the FTIR results. [ABSTRACT FROM AUTHOR]

A composite prepared from aerosil A380 and the liquid crystal (LC) 4-hexyl-4'-cyanophenyl benzoate (CP6B) was investigated by broadband dielectric spectroscopy in a large temperature range. The selected high silica density (ca. 7 g aerosil/1 g of CP6B) allows the observation of a thin layer (two-monolayer structure) adsorbed on the surface of the silica particles. For the composite one relaxation process is observed at frequencies much lower than that of the processes found for bulk CP6B. It is assigned to the dynamics of the molecules in the surface layer. The temperature dependence of its relaxation rates obeys the Vogel-Fulcher-Tammann law, which is characteristic for glass-forming liquids. The quasi 2D character of the observed glassy dynamics in the surface layer is discussed. The temperature dependence of the CP6B relaxation in the composite is compared with that of related hexylcyanobiphenyl molecules in the surface layer of aerosil composite with a similar concentration. [ABSTRACT FROM AUTHOR]

A new bis-imidazolium salt with two cyanobiphenyl groups and dodecyl sulfate counterion (BIC) was prepared by the metathesis reaction of the bromide salt with sodium dodecyl sulfate. The ILC shows at room-temperature a stable smectic A phase, confirmed by differential scanning calorimetry, polarized optical microscopy, and powder X-ray diffraction investigations. The ILC was doped with TiO 2 nanoparticles, having a high specific area, in concentrations of 0.1%, 0.2%, 1% and 2%. Broadband Dielectric Spectroscopy spectra have been registered in the (10−1–107) Hz frequency range, and (250–330) K temperature domain. The study shows that at constant frequency, the conductivity increases with the temperature and dopant concentration. The characteristic times of the observed relaxation processes showed a temperature variation according to the Vogel-Fulcher-Tammann law. Higher values of characteristic times were calculated at the increase of the thickness of the sample. On the other hand, the increase of the concentration of TiO 2 nanoparticles leads to a decrease of the characteristic relaxation times. In order to detect whether the obtained high permittivity increase is due to the Maxwell-Wagner or Electrode Polarization (EP) type phenomena, studies were made on samples of the same concentration, but different thicknesses, and EP was assigned as the main cause of this dielectric constant variation. Unlabelled Image • A new ionic liquid crystal was synthesized and doped with TiO 2 nanoparticles. • LC's ionic component has a dominant influence in the composite's conductivity. • Conductivity increased with temperature & dopant concentration, at constant frequency. • Electrode polarization phenomena are responsible for high increase in permittivity. • Relaxation time increases with sample thickness & decreases with TiO 2 concentration. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lanthanide complexes with N-substituted-4-pyridones ligands with mesogenic 3,4 or 3,5-di(alkyloxy)benzyl units. • The complexes show typical lanthanide solid state emission and lamellar phases (SmA). • Substitution pattern and length of flexible alkoxy chains control the phase-transition characteristics. • Dielectric spectroscopy was used to evaluate the dipolar relaxation processes and phase transitions. In the present work, new luminescent lanthanide complexes with extended mesomorphic range were prepared by coordination to lanthanide ions (Eu3+, Sm3+ and Tb3+) of the new 4-pyridone based organic ligands (L) with 3,4- (7- n ) and 3,5-di(alkyloxy)benzyl (8- n ) mesogenic groups and variable length (n = 12 or 14 carbon atoms) onto the benzyl unit. The cumulative results of the elemental analyses as well as the 1H, 13C NMR and IR spectroscopies support the structure of the organic derivatives and their lanthanide complexes [LnL 3 (NO 3) 3 ] (9- n /Ln and 10- n /Ln) described in this work. These complexes show characteristic lanthanide solid state emission, both at room and elevated temperatures corresponding to crystalline, glassy or liquid crystal states. The long range SmA phases displayed by all complexes were supported by a combination of characterization methods, including: differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and variable-temperature powder X-ray diffraction (XRD). This work shows that the number, substitution pattern and length of flexible alkoxy chains are important parameters to control the phase-transition characteristics of the lanthanide complexes. Complexes with 3,4-disubstituted pattern (9- n /Ln) show higher clearing temperatures (nearly 60 °C for Eu3+, 70 °C for Sm3+ and 85 °C for Tb3+ complexes) compared to their counterparts with 3,5-disubstituted pattern (10- n /Ln). Moreover, complexes 9- n /Ln crystallize when cooling their LC phase while complexes 10- n /Ln are stable in glassy state at room temperature as a consequence of the different close interdigitated molecular packing evidenced by XRD measurements. Dielectric spectroscopy was employed to detect the changes of order degree specific to each phases (crystalline, LC or isotropic). The variation of dielectric constant and the electrical conductivity versus temperature shows three transition intervals for selected complexes 10- 14 /Sm and 10 - 14 /Tb, which delimit the main intervals: 45–60 °C, 90–110 °C; 140–160 °C corresponding to the Cr 1 -Cr 2 , Cr 2 – SmA and SmA-Iso transitions, and agree very well with the DSC results. The change of characteristic time, obtained by Havriliak-Negami fit function, with temperature also provides a very good correlation with the DSC and POM results. [ABSTRACT FROM AUTHOR]