Oscillating materials1–4 that adapt their shape in response to an external stimulus are of interest for emerging applications in medicine and robotics. Liquid crystal networks have a prominent role in this area because they can be programmed to undergo stimulus-induced deformations in a variety of geometries, including in response to light5,6. In order to make these polymer networks photoresponsive, azobenzene molecules are often incorporated7–11. Most examples in the literature report on bending responses of these azobenzene modified films, where relaxation after photo-isomerization is rather slow. Modification of the core or addition of substituents to the azobenzene moiety can lead to drastic changes in photophysical and photochemical properties12–15 giving opportunity to circumvent the use of a complex set-up. Here we report on the incorporation of azo-derivatives with fast thermal relaxation into liquid crystal network films (LCN), to generate films that can exhibit continuous, directional macroscopic mechanical waves under constant light illumination, with a feedback loop driven by self-shadowing. A theoretical model and numerical simulation demonstrate this mechanism and show good qualitative agreement with experiments. We explore potential applications in light-driven locomotion and self-cleaning surfaces.

Hydrogen-bonded liquid crystalline polymers have emerged as promising “smart” supramolecular functional materials with stimuli-responsive, self-healing, and recyclable properties. The hydrogen bonds can either be used as chemically responsive (i.e., pH-responsive) or as dynamic structural (i.e., temperature-responsive) moieties. Responsiveness can be manifested as changes in shape, color, or porosity and as selective binding. The liquid crystalline self-organization gives the materials their unique responsive nanostructures. Typically, the materials used for actuators or optical materials are constructed using linear calamitic (rod-shaped) hydrogen-bonded complexes, while nanoporous materials are constructed from either calamitic or discotic (disk-shaped) complexes. The dynamic structural character of the hydrogen bond moieties can be used to construct self-healing and recyclable supramolecular materials. In this review, recent findings are summarized, and potential future applications are discussed.

Current developments in the field of thermotropic chiral-nematic liquid crystals as sensors are discussed. These one dimensional photonic materials are based on low molecular weight liquid crystals and chiralnematic polymeric networks. For both low molecular weight LCs and polymer networks, real-time and time integrating sensors have been realized. The response mechanism is either based on a change of helical twisting power of the dopant upon exposure to an analyte, or due to physical swelling, with a change of order in the liquid crystalline phase upon uptake of the analyte, causing the pitch to change.Sensors that respond to organic and water vapour, amines, water CO 2 , O 2 , metal ions, pH, strain and temperature have been reported.

We report on the fabrication of a rewritable and reprogrammable dual‐photoresponsive liquid crystalline‐based actuator containing an azomerocyanine dye that can be locally converted into the hydroxyazopyridinium form by acid treatment. Each dye absorbs at a different wavelength giving access to programmable actuators, the folding of which can be controlled by using different colors of light. The acidic patterning is reversible and allows the erasing and rewriting of patterns in the polymer film, giving access to reusable, adjustable soft actuators.

Via an isocyanate-free route, a series of segmented polyureas (PUs) were synthesized from (potentially) renewable resources. To the best of our knowledge, the present work shows for the first time that the organic superbase guanidine 1,5,7-triazabicyclododecene (TBD) which was originally developed as a catalyst for the ring-opening polymerization of lactones, lactides or cyclic carbonates, is also a promising catalyst for the transurethanization between dicarbamates and diamino-terminated poly(propylene glycol) (PPGda) providing PUs via an isocyanate-free strategy. The renewable segmented PUs contain monodisperse hard segments (HSs). This well-defined structure was verified by the DMTA plots of the PUs, showing a sharp glass transition, a sharp flow transition and a flat rubbery plateau. The flow and maximum use temperature (Tfl ) of the PUs increases with the increasing number of urea groups in the corresponding dicarbamates. In addition, at constant HS length, the length of the soft-segment (SS) can be changed to adjust the properties of the PU materials, enabling their application as adhesives, soft elastomers, or rigid plastics.

Many publications report on stimuli responsive coatings, but only a few on the controlled release of species in order to change the coating surface properties. A sponge-like coating that is able to release and absorb a liquid upon exposure to light has been developed. The morphology of the porous coating is controlled by the smectic liquid crystal properties of the monomer mixture prior to its polymerization, and homeotropic order is found to give the largest contraction. The fast release of the liquid can be induced by a macroscopic contraction of the coating caused by a trans to cis conversion of a copolymerized azobenzene moiety. The liquid secretion can be localized by local light exposure or by creating a surface relief. The uptake of liquid proceeds by stimulating the back reaction of the azo compound by exposure at higher wavelength or by thermal relaxation. The surface forces of the sponge-like coating in contact with an opposing surface can be controlled by light-induced capillary bridging revealing that the controlled release of liquid gives access to tunable adhesion.

Photoresponsive nanoporous polymer films have been fabricated by adding a photoresponsive azobenzene cross-linker to a hydrogen-bonded smectic liquid crystalline polymer network. A base treatment resulted in the nanoporous material which has been fully characterized. Upon exposure to UV light a decrease in the smectic layer spacing is observed, suggesting a decrease in pore size. In addition, the binding sites in the material could be changed with light, leading to light-induced adsorption of cations and cationic dyes. Finally, light could also be used to create nanoporous channels in the polymer film.

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.