Hydrogen Bond Enhances Photomechanical Swing of Liquid-Crystalline Polymer Bilayer Films.

Abstract

Mechanical swing is common in nature, such as sound waves, wingbeat of birds, and heartbeat, which is important to convert input energy into continuous motion. Here, we report a photodriven swing actuator composed of commercially available polyimide (Kapton) and azobenzene-containing liquid-crystalline polymers. The liquid-crystalline polymers act as the photoactive layer, which were synthesized by copolymerization of one benzenecarboxylic acid-containing monomer (M6BCOOH) and one azobenzene-containing monomer (M6ABOC2) with different molar ratios. The Kapton layer with a high elastic modulus is photoinert and functions as the substrate layer. After thermal annealing, the film displays chaotic swing under continuous irradiation of actinic light. Interestingly, the swing amplitude is greatly enhanced by the existence of supramolecular hydrogen bonding in liquid-crystalline polymer films. It is the introduction of M6BCOOH to the copolymer that accelerates the trans-cis photoisomerization rate of azobenzenes. Also, it forms a hydrogen bond as physical crosslinking sites, enabling the polymer film to work as a whole. Thus, it enhances the driving force for photomechanical deformation. Moreover, it improves the elastic modulus of the photoactive layer and modulates the swing behavior of the bilayer strip. More importantly, the formation of a hydrogen bond in the form of acidic dimers has a spatial confinement effect, extending the timescale of photodriven swing. The photomechanical self-vibration of the bilayer film can be ascribed to the combination of the photoisomerization process of azobenzenes with the local photosoftening effect of liquid-crystalline polymers.