Short bent-core molecules: X-ray, polarization, dielectricity, texture and electro-optics investigations.

Bent-core liquid crystals based on 1,2,4-oxadiazole as a central unit have been the first mesogens to exhibit a ferroelectric response in the nematic phase. This behavior has been widely recognized as due to the presence of smectic-like polar cybotactic clusters permeating the nematic phase. Unfortunately, these compounds exhibited rather high melting points, about 120 °C, due to the presence of four benzene rings in the molecules. Here we describe the synthesis and physical characterization of a new series of BC mesogens, featuring the same bent core as the previous compounds but shorter outer substituents. By keeping only two benzene rings, we were able to lower the melting points to about 70 °C. However, while X-ray diffraction and dielectric spectroscopy measurements confirm the cybotactic nature of the nematic phase of these compounds, polarization and electro-optical measurements ascribe their polar response to flexoelectricity rather than to spontaneous polarization. Finally, texture investigation suggests the biaxiality of the nematic phase, which is indicated also by conoscopic measurements. These results are important for recognizing size and rigidity limitations in designing bent-core liquid crystal molecules suitable for applications.

Optical nonlinearity in the nematic phase of bent-core mesogens.

Nonlinear optical response of the cybotactic nematic phase of a bent-core mesogen has been investigated for the first time through self-phase modulation induced by a Gaussian beam. The material exhibits a high nonlinear response achieving a nonlinear index n(2)≈5×10(-5) cm(2)/W and an unconventional behavior characterized by two different regimes. While the high-intensity regime can be easily explained in terms of a thermal indexing effect, the low-intensity regime is metastable and characterized by an unusual dependence on the irradiation energy. It is suggested that a change of the director configuration, possibly due to a light-induced modification of surface anchoring, is responsible for the observed behavior.

Optical and mechanical shrinkage effects in dye-doped photonic bandgap structures based on organic materials.

In this work we study the effects of the optical shrinkage in polymer and liquid crystal (LC) mixtures optimized for their use as active media in compact plastic laser devices. These mixtures are characterized by the presence of the rhodamine 6G as an active dye. Modifications in the reflection properties of the gratings as a function of the active dye concentration have been determined experimentally and a detailed theoretical simulation of the optical transmittance properties of these devices is provided. Moreover, the comparison between two different experimental approaches clarifies the contribution to the optical shrinkage due to the presence of the active dye. In principle this approach allows determining the linear mechanical shrinkage by separating the contribution to optical shrinkage due to photochemical transformations from that due to mechanical effects.

Light-induced molecular adsorption and reorientation at polyvinylcinnamate-fluorinated/liquid-crystal interface.

We have carried out a detailed experimental study, by means of x-ray reflectometry (XRR) and half-leaky guided mode (HLGM) optical characterization, of the light-induced molecular adsorption and reorientation at the polyvinylcinnamate-fluorinated (PVCN-F)/liquid-crystal (LC) interface of a LC cell doped with the azo-dye methyl red (MR). The XRR data allowed characterizing the microscopic structure of the adsorbed dye layer both before irradiation (dark adsorption) and after irradiation (light-induced adsorption). The HLGM optical characterization has made possible the experimental determination of the nematic director profile in the LC cell and evaluation of the effects of light-induced adsorption on the LC anchoring conditions. The experimental findings have confirmed the formation of a dark-adsorbed layer and are in agreement with the absorption model previously proposed to account for the complex phenomenology related to light-induced anchoring and reorientation in dye-doped liquid crystals.

On the origin of the huge nonlinear response of dye-doped liquid crystals.

We report the results of an investigation carried on Methyl Red-doped nematic liquid crystals with the aim of studying the basic mechanism of the extraordinarily large nonlinear response recently reported. We show that the experimental data can be explained as due to light-induced modifications of the anchoring conditions leading to director reorientation on the irradiated surface, which in turn gives rise to a bulk reorientation through the cell. We have called this phenomenon SINE (Surface Induced Nonlinear Effect) to remind that it occurs "without" (= sine in latin language) a direct optical or electric torque on the director in the bulk.

Structure of self-assembled liposome-DNA-metal complexes.

We have studied the structural and morphological properties of the triple complex dioleoyl phosphatidylcholine (DOPC)-DNA-Mn2+ by means of synchrotron x-ray diffraction and freeze-fracture transmission electron microscopy. This complex is formed in a self-assembled manner when water solutions of neutral lipid, DNA, and metal ions are mixed, which represents a striking example of supramolecular chemistry. The DNA condensation in the complex is promoted by the metal cations that bind the polar heads of the lipid with the negatively charged phosphate groups of DNA. The complex is rather heterogeneous with respect to size and shape and exhibits the lamellar symmetry of the L(c)(alpha) phase: the structure consists of an ordered multilamellar assembly similar to that recently found in cationic liposome-DNA complexes, where the hydrated DNA helices are sandwiched between the liposome bilayers. The experimental results show that, at equilibrium, globules of the triple complex in the L(c)(alpha) phase coexist with globules of multilamellar vesicles of DOPC in the L(alpha) phase, the volume ratio of the two structures being dependent on the molar ratio of the three components DOPC, DNA, and Mn2+. These complexes are of potential interest for applications as synthetically based nonviral carriers of DNA vectors for gene therapy.

Photo-orientation of liquid crystals due to light-induced desorption and adsorption of dye molecules on an aligning surface.

We show that adsorption of dye molecules control the light-induced alignment of dye-doped nematic liquid crystal (LC) on a nonphotosensitive polymer surface. The dependencies of light-induced twist structures on exposure, thermal baking, thickness, and aging before irradiation of the LC cells allowed us to propose the following mechanism for the alignment. Before irradiation, the "dark"-adsorbed layer on the tested surface is formed from dye molecules predominantly aligned along the initial direction of the director. Irradiation of the cell with linearly polarized light produces an additional layer with different orientational ordering of dye molecules. The final easy axis is determined by the competition of "dark" and light-induced contributions to anchoring and is aligned between the "dark" easy axes and polarization of the light. For quantitative interpretation, we apply the tensor model of anchoring and assume that the photoalignment in the mesophase is a cumulative effect of the light-induced anchoring on the background of the already existing anisotropic "dark" dye layer.

Hidden photoalignment of liquid crystals in the isotropic phase.

We found the effect of a hidden photoalignment of a dye-doped nematic liquid crystal (LC) on a nonphotosensitive polymer surface after polarized irradiation of the cell in the isotropic phase. We observed that irradiation resulted in a uniform planar orientation of the LC after cooling to the mesophase. The direction of a light-induced easy axis on the polymer can be either parallel or perpendicular to the polarization of the incident light, depending on the light intensity. We attribute this behavior to two mechanisms of photoalignment: light-induced adsorption of dye molecules on the substrate, and anisotropic desorption in a previously adsorbed dye layer. The experimental results on photoalignment of a LC on a thin dye film confirm our model.

Structural studies on layered alkylpyridinium iodopalladate networks.

The reaction of alkylpyridinium (CnH2n + 1NC5H5, hereafter Cn-Py) iodide salts in aqueous acetonitrile with a preformed palladium iodide precursor afforded two different types of organic-inorganic phases depending on the molar ratio. A 2:1 ratio yielded the phase [Cn-Py]2[PdI4] (3, n = 14, 16), which crystallized in the triclinic crystal system. The X-ray crystal structure of 3, (n = 14), refined in the space group P1 (a = 8.918(3) A, b = 9.894(3) A, c = 29.062(12) A, alpha = 93.51(3) degrees, beta = 94.17(3) degrees, gamma = 115.60(3) degrees, and Z = 2), consists of interdigitated bilayers with a basal spacing of 29.0 A. The aliphatic chains of the cations, which run almost parallel to the stacking direction, are fully stretched between polar planes built on isolated [PdI4]2- anions and cation headgroups. Changing the organic cation to palladium ratio to 1:1 led to a new phase [Cn-Py]2[Pd2I6] (4, n = 14, 16), which crystallizes in the triclinic P1 space group (a = 9.399(4) A, b = 14.264(6) A, c = 29.415(13) A, alpha = 92.11(4) degrees, beta = 90.07(4) degrees, gamma = 104.53(3) degrees, Z = 3 for 4(n = 14); a = 9.417(2) A, b = 14.215(3) A, c = 31.552(6) A, alpha = 87.96(3) degrees, beta = 87.63(3) degrees, gamma = 75.67(3) degrees, Z = 3 for 4(n = 16)). The layered structure is basically of a continuously interdigitated single-layer type, with a bilayer sublattice superimposed. Isolated [Pd2I6]2- anions contribute to the inorganic planes. A high degree of interdigitation and tilting of the aliphatic chains lead to basal spacings of 29.4 and 31.5 A for 4(n = 14) and 4(n = 16), respectively. The [Cn-Py]2[PdI4] and [Cn-Py]2[Pd2I6] phases were characterized by thermal analysis. Mesomorphic behavior was observed only for 3(n = 16), which was confirmed by variable-temperature powder XRD and optical microscopy.

Dye-doped liquid crystals as high-resolution recording media.

Light-induced anchoring of the molecular director is reported to be an efficient method for writing permanent holographic gratings in dye-doped liquid crystals. We have achieved higher sensitivity and spatial resolution in these materials with other methods. An energy density as low as 10(-1) J/cm(2) was sufficient to write gratings with a resolution higher than 100 lines/mm.

Dye-doped liquid crystals as high-resolution recording media: errata.

In Ref. 1, the second sentence of the abstract should read as follows: "As compared with other methods that make use of these materials, we have achieved higher sensitivity with good spatial resolution."

Surface reorientation induced by short light pulses in doped liquid crystals.

Fast surface reorientation induced by a single 4-ns low-energy laser pulse in dye-doped liquid crystals is reported. The reorientation is due to light-induced modification of the surface anisotropy, which affects the liquid crystal's director through the appearance of a preferred direction on the irradiated surface. The detected signals can be interpreted as being the result of light-induced desorption and adsorption of dye molecules.