Interactions of phenolic and carboxylic groups containing chromophores (hydroxyarylidene alkanones) with polyamidines were investigated with ultraviolet-visible spectroscopy and dynamic light scattering experiments. Because of the strong basicity of the polyamidines, deprotonation of the chromophores was observed. The ionic network formation process depended on the method of the complex preparation. The step-by-step addition of the chromophore to an excess of polyamidine led to the incorporation of the dye molecules inside the polymer coil, and only after this did the interaction of surface functional groups with an additional amount of the low-molecular-weight compound lead to network formation. The interaction of the polymer with an excess of the dye initially led to the saturation of amidine groups by chromophore molecules and network formation without the complete destruction of the dye packs. The molecular structure proposed for these complexes was examined with experimental data. (C) 2005 Wiley Periodicals, Inc.