Liquid-crystalline (LC) phase behavior and photoinduction of optical anisotropy in the ionic self-assembly complex 4-(4-diethylaminophenylazo) benzenesulfonate-dimethyldidodecylammonium $\left(\mathrm{EO}\text{−}{\mathrm{C}}_{12}\mathrm{D}\right)$ 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-$A$ $\left({\mathrm{sm}A}_2\right)$ LC phase at elevated temperatures $(65–160°\mathrm{C})$ and in a rectangular columnar $\left({\mathrm{Col}}_{\mathrm{r}}\right)$ LC phase in the temperature range of $-5–65°\mathrm{C}$. 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 (${\mathrm{Ar}}^{+}$ laser, $\lambda =488\mathrm{nm}$). 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.

• Received 15 September 2006

DOI:https://doi.org/10.1103/PhysRevE.75.031703