A tertiary amine functionalized 4-nitro-4'-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S-A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase. (C) 2007 Elsevier Ltd. All rights reserved.