Photoactive Fluorinated Poly(azomethine)s with Azo Groups in the Main Chain for Optical Storage Applications and Controlling Liquid Crystal Orientation

Polymer multicomponent materials containing conjugated fragments (such as azo- or azomethine groups) have attracted significant attention due to their possible use in the efficient reversible stimuli-responsive, light-responsive devices. Light-responsive polyazomethines with azo groups in the backbone (Azo-Pams) are synthesized by polycondensation of tetrafluorobenzene- or octafluorobiphenylene-based bis-hydroxybenzaldehydes with hexamethylenediamine. The polymers feature the simultaneous combination of azo and azomethine groups inside one conjugated block. The synthesized polymers can be solution cast into flexible solid films with tensile strength of about 24 MPa. We found that the obtained Azo-Pam polymers have an amorphous structure (Tg ∼ 134 °C) and high thermal stability (up to 300 °C). Their optical spectra depend on the solvent type and its pH which influence the dynamical equilibrium between the tautomeric forms. It also determines the balance between the main (azo form) and the ionized form in the solvent and allows to purposefully regulate the absorption maxima. We demonstrate the ability to record optical information using Azo-Pam films in the form of polarization gratings (holograms) with a regulated diffraction efficiency. A uniform orientation of liquid crystal is achieved by a polarized UV irradiation of glass substrates covered with the polymer Azo-Pam-II. The obtained data show that the synthesis strategy of the Azo-Pam polymers is an effective instrument for designing a wide range of stimuli-responsive and optical active materials.