ABSTRACT
Liquid-crystalline (LC) phase behavior and photoinduction of optical anisotropy in the ionic self-assembly complex 4-(4-diethylaminophenylazo) benzenesulfonate-dimethyldidodecylammonium (EO-C12D) has been investigated by polarized light microscopy, differential scanning calorimetry (DSC), x-ray scattering, null-ellipsometry, and UV-visible absorbance techniques. The complex exists in a bilayer smectic- A (smA{2}) LC phase at elevated temperatures (65-160 degrees C) and in a rectangular columnar (Col{r}) LC phase in the temperature range of -5-65 degrees C . Hysteresis in the transition from the smectic to the columnar LC phase was observed. Detailed experimental investigations of the phase behavior, film-forming properties, and induction of optical anisotropy were performed. High values of photoinduced anisotropy (dichroic ratio of approximately 50) were detected when thin films of the complex were irradiated with linearly polarized light ( Ar+ laser, lambda=488 nm ). It was shown that the azobenzene units align perpendicular to the polarization of the exciting light causing an alignment of the columns parallel to the light electric field vector. On the basis of all experimental results a model of the photoinduced alignment of the photochromic complex is proposed in which photoalignment of the material is connected to the reorientation of domains.
ABSTRACT
Liquid-crystalline properties of the ionic self assembled complex benzenehexacarboxylic- (didodecyltrimethylammonium)6 [BHC- (C12D)6] were investigated by polarizing microscopy, differential scanning calorimetry (DSC), x-ray analysis, null ellipsometry, UV and IR spectroscopy. The complex exhibits a bilayer smectic Sm- A2 liquid-crystalline phase and aligns spontaneously. Alignment properties do not depend on the hydrophobic or hydrophilic treatment of the surfaces. The aligned complex possesses a negative (delta n=-0.02) homeotropically oriented optical axis, with layers aligned parallel to the surface. X-ray analysis of the aligned sample revealed a lamellar structure with a d spacing of 3.15 nm, consisting of sublayers of thicknesses d1 = 1.41 and d2 = 1.74 nm . This was confirmed by simple geometrical calculations and detailed temperature-dependent investigations, revealing that the first layer contains the BHC molecules and oppositely charged groups of the surfactants, and the second the alkyl tails of the surfactant. Changes in the order parameters (as calculated from the IR investigations) are correlated with the phase transitions as found by DSC. The properties of the complex are strongly influenced by the ionic interactions within the complex. The presence of these groups slows down the dynamics within the material sufficiently to allow for crystallization of the complex from an aligned LC phase into a single crystal domain, as well as restricting the transition to the isotropic phase.
