The multicolour fluorescence responses to external mechanical forces vs. internal photomechanical stresses of a molecular solid are demonstrated and compared.
For microscale 4D photoresponsive actuators, light is crucial in two ways. First, the underlying additive manufacturing techniques rely on photopolymerization processes triggered by the absorption of light. Second, the absorption of light serves as the actuation stimulus. The two absorptions can be conflicting. While the microstructure requires strong absorption at the actuation wavelength(s), this absorption should not interfere with that of the manufacturing process. Herein, a simple strategy is proposed to overcome these limitations and allow for the fabrication of multi‐photoresponsive 3D microstructures that can be actuated at different wavelengths of light. Two‐photon 3D laser printing is selected as the fabrication technique and liquid crystalline (LC) elastomers as the functional materials. In a first step, 3D microstructures are fabricated using an aligned LC ink formulation. Thereafter, up to five different dyes exhibiting absorptions that extend over the entire visible regime (400–700 nm) are successfully incorporated into the LC microstructures by an exchange process enabling a programmable actuation by irradiating with the suitable wavelength. Furthermore, by combining dyes exhibiting orthogonal absorptions, wavelength‐selective actuations are demonstrated.
based on a reversible phase transition at the lower critical solution temperature (LCST) due to a globule-to-coil transition. [8] Below the LCST the polymer is in a hydrophilic, hydrated state, while above the LCST it is in a hydrophobic state. In this state, the interactions of the polymer with itself lead to a higher gain in free energy than would be achieved by solvation energy. The volume of pNIPAM materials in the hydrated, swollen state is much higher than in the hydrophobic state, because water is integrated into the material in the hydrated state. [9] As the actuation of pNIPAM hydrogel is based on its water-dependent shrinkage and swelling, the actuation efficiency and the forces generated by pNIPAM-based actuators critically depend on the in-and outflow of water through the pores of the material. Therefore, the actuation effect, including actuation dynamics as well as stroke forces, can be improved by introducing pores into the material. [10,11] Whereas in previous studies template-assisted methods have proven highly suitable for introducing pores into hydrogels, they lack local microstructural control, while being excellent for structuring macroscopic samples with an interconnected structure. [10] For generating highly efficient pNIPAM-based microactuators, a precisely defined design is required and thus methods are needed that allow for their highly precise 3D structuring at the micrometer scale.The technology of additive nano-and micromanufacturing opens doors to novel and remarkable microengineering possibilities and even enables printing of simple 3D volumetric structures at small scales. [12] Direct laser writing (DLW) involving two-photon polymerization of photoresists is one of the additive manufacturing techniques that can be used to fabricate intricate and miniaturized 3D structures, as they are required for the fabrication of microactuators. By utilizing twophoton absorption and a femtosecond pulsed laser, this fabrication method allows to print in sub-micrometer resolution, even with several materials and on different types of substrates. [13,14] Direct laser writing has also proven highly suitable for fabricating 4D materials, i.e., responsive materials that change their properties due to an external stimulus. [15] For example, the shape of such materials could be controlled at the micrometer scale by temperature and light. [16] Thermoresponsive hydrogels such as poly(N-isopropylacrylamide) (pNIPAM) are highly interesting materials for generating soft actuator systems. Whereas the material has so far mostly been used in macroscopic systems, here it is demonstrated that pNIPAM is an excellent material for generating actuator systems at the micrometer scale. Two-photon direct laser writing is used to precisely structure thermoresponsive pNIPAM hydrogels at the micrometer scale based on a photosensitive resist. This study systematically shows that the surface-to-volume ratio of the microactuators is decisive to their actuation efficiency. The phase transition of the pNIPAM is also demonstrated...
Molecular photoswitches are widely used in material sciences, physics, chemistry, and biology. As needs grow more complex, materials have to react more than one‐dimensionally. The use of multiple photoswitches at once opens manifold opportunities for further improved and more complicated systems. However, this requires independent addressability, i.e., orthogonality, and reversible processes. Herein, the first study on ultrafast excited state dynamics of two orthogonal photoswitches, a push‐pull azobenzene and a donor‐acceptor Stenhouse adduct is reported. In order to gain detailed insight in their interactions and mutual influences on their photoswitching behavior, they are addressed individually and simultaneously via transient absorption spectroscopy supported by quantum chemical calculations. They show reversible photoswitchability and in addition, can be used in 4D printing to provide easy access to a plethora of functional devices. Furthermore, environmental influences on the excited state dynamics are examined using different solvents and thin films. Both compounds photoisomerize independently when addressed individually or simultaneously and only little impacts on the excited state dynamics are found. Especially the vibrational relaxation is affected by different surroundings changing the energy dissipation while hardly affecting the electronic states involved. The orthogonal and simultaneous addressability is thereby crucial for their usage in 4D printed microactuators.
Advances in soft robotics strongly rely on the development and manufacturing of new responsive soft materials. In particular, light‐based 3D printing techniques, and especially, digital light processing (DLP), offer a versatile platform for the fast manufacturing of complex 3D/4D structures with a high spatial resolution. In this work, DLP all‐printed bilayered structures exhibiting reversible and multi‐responsive behavior are presented for the first time. For this purpose, liquid crystal elastomers (LCEs) are used as active layers and combined with a printable non‐responsive elastomer acting as a passive layer. Furthermore, selective light response is incorporated by embedding various organic dyes absorbing light at different regimes in the active layers. An in‐depth characterization of the single materials and printed bilayers demonstrates a reversible and selective response. Last, the versatility of the approach is shown by DLP printing a bilayered complex 3D structure consisting of four different materials (a passive and three different LCE active materials), which exhibit different actuation patterns when irradiated with different wavelengths of light.
The interplay of mechanical grinding and aniline vapor fuming on the fluorescence of the pentiptycene-anthracene-pentiptycene π-conjugated molecules PAP-Cn, where n is 4, 8, 12, or 16 and refers to the number of carbon atom in the terminal alkyl chains, in solid films are reported. The differences and similarities among the four homologs have led to a conclusion of the formation of an emissive triplex state for the ground and fumed films. Thermogravimetric analysis reveals the guest-host molar ratio and the retention ability of the aniline on the various types of films. A stepwise protocol of fuming-grindingannealing is developed for fluorimetric differential sensing of eight substituted aniline vapors with a single probe of PAP-C8. The role of the bulky pentiptycene groups in the observed fluorescence properties is also discussed.
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