O. Francescangeli

Dye-doped photorefractive liquid crystals for dynamic and storage holographic grating formation and spatial light modulation

The basic mechanisms of photo-induced space charge field formation, director axis re-orientation, and refractive index changes in fullerene C60- and dye-doped nematic liquid crystals films are presented. In particular, in aligned methyl-red-doped nematic liquid crystal film, we observe a nonlinear index change coefficient as high as 10 cm/sup 2//W, associated with purely optically induced liquid crystal director axis re-orientation. Experimental observations of dynamic and high-resolution storage holographic grating formation, two beam coupling with gain of nearly 3000 cm/sup -1/, optical limiting action at nanowatt cw laser power, and incoherent-coherent image conversion at /spl mu/W/cm/sup 2/ light intensity level are discussed.

NEW HYBRID NANOCOMPOSITES BASED ON AN ORGANOPHILIC CLAY AND POLY(STYRENE-B-BUTADIENE) COPOLYMERS

The preparation, by direct melt intercalation, and the properties of new hybrid organic-inorganic nanocomposites, consisting of a commercial sample of poly(styrene- b -butadiene) copolymer (SBS) and a commercial organophilic clay containing the dioctadecyl dimethyl ammonium salt are described. In addition, several mixtures between the same copolymer and an unfunctionalized clay were prepared and studied. XRD spectra showed a partial insertion of the SBS block copolymer segments in the interlayers of the organophilic clay, accompanied by a loss of correlation within the layers. The degree of insertion increased by annealing the nanocomposites at 120 °C for increasing time periods. No interaction between the polymer matrix and the unfunctionalized clay was found. The storage modulus value, in the plateau region between the glass transition processes of the polybutadiene and the polystyrene blocks, and the glass transition temperature of the polystyrene block domain increase as both the organophilic clay content and the annealing time increase. The glass transition process of the polybutadiene block domain is practically unaffected by the filler content and the annealing treatments. These data are most promising for upgrading the thermo-mechanical behavior and the application temperature window of the SBS thermoplastic elastomers through the preparation of nanocomposites employing suitably designed organophilic clays.

Effects of light on molecular orientation of liquid crystals

A review of basic physical phenomena underlying the light-induced molecular reorientation in nematic liquid crystals is presented. A detailed description of the mechanisms of direct optical torque, photoisomerization and photorefractivity and of their effect on the macroscopic order of liquid crystals is reported. The first part of the article deals with the study of reorientation effects in transparent liquid crystalline materials. Here, the effects of photo-induced molecular reorientation are fully interpreted within the framework of classical electrodynamics and standard continuum theory of liquid crystals. We investigate the peculiar properties related to the macroscopic anisotropy and the collective behaviour of liquid crystals that result in extraordinarily large nonlinear optical response. Afterwards, the behaviour of liquid crystals in the presence of light absorption is considered and the related reorientation effects are discussed. We give a review of the wide phenomenology which is met in liquid crystals when doped with absorbing azo-dye molecules. The photoisomerization process that in this case drives the evolution of the dye-liquid crystal mixture consequent to the interaction with the light is discussed in detail. Finally, the relatively new field of photorefractivity in liquid crystals as a source of molecular reorientation is considered. We describe the different mechanisms contributing to the creation of a space-charge field such as conductivity anisotropy, dielectric anisotropy and photocharge production. A theoretical discussion of the fundamental mechanisms regulating the dc-field-assisted optically induced space-charge fields and the optical molecular reorientation in nematic liquid crystal films is also given.

Insights into the cybotactic nematic phase of bent-core molecules

We present X-ray diffraction evidence for clusters exhibiting a skewed cybotactic supramolecular structure in the nematic phase of the butyloxy-phenyl diester, ODBP-Ph-OC4, a bent core mesogenic diester of the nonlinear diol 2,5-bis-(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). The temperature dependence of the off-meridional four-spot pattern shows that the tilt angle in the cybotactic clusters changes with temperature. The correlation lengths exhibit no evidence of critical behavior but there is no underlying smectic C phase in ODBP-Ph-OC4. The tilted cybotactic clusters persist throughout the 85 °C wide nematic phase, and even remain evident in the supercooled nematic. This inherently biaxial supramolecular structure—clusters of stratified and tilted mesogens—embedded in an otherwise translationally disordered nematic host medium may account for the NMR biaxiality observed in nematic phases of ODBP mesogens.

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.

Crystal architecture and mesophase structure of long-chain N-alkylpyridinium tetrachlorometallates

The N -hexadecylpyridinium derivatives [C16Py] 2 [MCl 4 ] (M=Cd ( 1 ), Zn ( 2 )) were prepared and structurally characterized by X-ray diffraction methods. The crystal structure of 1 reveals a layered arrangement with alternation of monolayers of interdigitated cations with layers of isolated [CdCl 4 ] 2− anions. CH⋯ClCd interactions reinforce the association between anions and cations in the polar region of the supramolecular structure. Both 1 and 2 display a thermotropic smectic A phase in addition to some high-temperature crystalline modifications. The thermal polymorphism of the salts was studied by X-ray powder diffraction, differential scanning calorimetry (DSC), and thermal optical microscopy. The structural and mesomorphic characteristics of 1 and 2 are compared with those of the analogous salts along the series [C16Py] 2 [MCl 4 ] (M=Co, Ni, Cu, Zn, Pd, Cd).

Cybotaxis dominates the nematic phase of bent-core mesogens: a small-angle diffuse X-ray diffraction study

New temperature dependent X-ray diffraction (XRD) data on the bent-core mesogens based on the nonlinear 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP) unit enable a consistent interpretation of the supramolecular structure in this class of liquid crystals. Strong evidence for cybotaxis in the high temperature phase explains the small-angle four-spot pattern and calls into question prior XRD interpretations. We find that the data can be satisfactorily explained by skewed cybotaxis, a stratified arrangement of tilted, bent-core mesogens (BCMs). We also observe the temperature-induced evolution of skewed cybotaxis to normal cybotaxis—strata wherein the long axes of the BCMs are normal to the layer fluctuations. Our XRD interpretation is compatible with the NMR data that exhibit biaxiality in the nematic phase of ODBP mesogens.

Dinuclear cyclopalladated azobenzene complexes : a comparative study on model compounds for organometallic liquid-crystalline materials

The series of dinuclear 4,4′-bis(hexyloxy)azobenzene, [H(Azo-6)], cyclopalladated complexes of general formula [Azo-6)Pd(µ-X)]2, (X = Cl, Br, I, N3, SCN, OAc) and [Azo-6)2Pd2(µ-Ox)] (Ox = oxalate) have been synthesized and investigated for mesomorphism and spectroscopic properties. Single-crystal X-ray analysis of the dinuclear bromo- and iodo-bridged complexes has been performed. The structural data, compared with those of the known homologous chloro compound, show that all the [Azo-6)Pd(µ-X)]2)] (X = Cl, Br, I) molecules crystallize in the monoclinic space group P21/c and are isomorphous. They are arranged in slipped pairs with intermolecular non-bonding Pd–Pd contacts ranging from 3.668(1) A(X = Cl) to 3.758(3) A(X = I). The different nature of the bridging group allows variation of the distance between the palladium atoms and the bond environment experienced by the metal centers. Thus, this comparative study reveals that the effectiveness of the bridging group in promoting thermotropic mesophases is greater for chloride, bromide, azide or oxalate than for iodide, thiocyanate or acetate. The greatest range of liquid-crystal behavior was displayed by [Azo−6)2Pd2(µ−Ox)]. Remarkably, this compound is the first example of a metallomesogen containing the bridging oxalate group. The bimetallic complexes exhibit different absorption spectra (i.e. colors) depending, in general terms, on the nature of the bridge connecting the two cyclometalated [H(Azo-6)] moieties, which can be varied so as to tune the optical properties. Blocking the azo group in the trans position results in several cases in weakly luminescent complexes, with luminescence efficiencies ϕ ≈10−4 and luminescence lifetimes of the order of nanoseconds. Using the data obtained from the 4,4′-bis(hexyloxy)azoxybenzene [H(Azoxy-6)] derivative, [Azoxy-6)Pd(µ -Cl)]2, from the mononuclear acetylacetonate (acac) complexes [(Azo-6)Pd(acac)] and [(Azoxy-6)Pd(acac)], and from the uncomplexed [H(Azo-6)] and [H(Azoxy-6)] ligands, the nature of the excited states relevant to the photophysical behavior are discussed. Copyright

HIGH RESOLUTION POLARIZATION GRATINGS IN LIQUID CRYSTALS

Efficient recording of polarization gratings in dye-doped liquid crystals is reported. By exploiting the effect of light-induced anchoring of the molecular director, it has been possible to write stable holographic gratings with a diffraction efficiency of 8% at a resolution of 1000 lines/mm. The required surface energy density of 0.3 J/cm2 sets these materials among the most sensitive for optical storage.

Banana-shaped 1,2,4-oxadiazoles

Abstract3,5-Disubstituted 1,2,4-oxadiazoles are a new type of liquid crystalline (LC) compounds with asymmetrical five-membered heterocycle as a central unit. They have a bent shape and are very convenient model-compounds for studying the dependence of the LC properties on the molecular design. We have also synthesized and investigated ‘banana-shaped’ 1,2,4-oxadiazoles using the ester groups as the linkage units. The new compounds exhibit spontaneous polarization in the smectic phase, even if there is no chiral group in the molecules. Preliminary experimental data suggest the presence of spontaneous polarization in the nematic phase as well. In order to study the structural properties of the LC phases, X-ray diffraction (XRD) measurements on powder samples have been carried out. Based on the XRD data, a model of the structural arrangement of the bent molecules in the smectic phase is provided, which accounts for the macroscopic spontaneous polarization as well as the ferroelectric switching behavior.