Search Results (13)

This work aims to determine the mechanism of the photomechanical response of poly(Methyl methacrylate) polymer doped with the photo-isomerizable dye Disperse Red 1 using the non-isomerizable dye Disperse Orange 11 as a control to isolate photoisomerization. Samples are free-standing thin films with thickness that is small compared with the optical skin depth to assure uniform illumination and photomechanical response throughout their volume, which differentiates these studies from most others. Polarization-dependent measurements of the photomechanical stress response are used to deconvolute the contributions of angular hole burning, molecular reorientation and photothermal heating. While photo-isomerization of dopant molecules is commonly observed in dye-doped polymers, the shape changes of a molecule might not couple strongly to the host polymer through steric mechanical interactions, thus not contributing substantially to a macroscopic shape change. To gain insights into the effectiveness of such mechanical coupling, we directly probe the dopant molecules using dichroism measurements simultaneously while measuring the photomechanical response and find mechanical coupling to be small enough to make photothermal heating—mediated by the transfer of optical energy as heat to the polymer—the dominant mechanism. We also predict the fraction of light energy converted to mechanical energy using a model whose parameters are thermodynamic material properties that are measured with independent experiments. We find that in the thin-film geometry, these dye-doped glassy polymers are as efficient as any other material but their large Young’s modulus relative to other organic materials, such as liquid crystal elastomers, makes them suitable in applications that require mechanically strong materials. The mechanical properties and the photomechanical response of thin films are observed to be significantly different than in fibers, suggesting that the geometry of the material and surface effects might play an important role. Full article

Azo-containing liquid crystal elastomers are photomechanical materials that can be actuated via illumination. The photomechanical response is a result of the photoisomerization of the azo moiety, which produces bulk stresses in the material. These stresses arise via two distinct and competing mechanisms: order parameter change induced stress and direct contractile stress. We describe thermomechanical and photomechanical experiments aimed at assessing the relative contributions of these. We show that the details of the attachment of azo dyes to the network can greatly influence the photoresponse. We discuss our results and summarize our findings. Full article

Photomechanical molecular crystals, actuated by solid-state photochemical reactions, manifest a spectrum of mechanical motions upon light exposure, underscoring their prospective integration into the next generation of intelligent materials and devices. Utilizing the solid-state photodimerization of naphthyl acrylic acid as a paradigm, this study delved into the interplay between crystal morphology and reaction dynamics on the photomechanical responses of molecular crystals. Distinct crystal forms—bulk, microrods, and microplates—were cultivated through tailored crystallization conditions. While bulk crystals of naphthyl acrylic acid (NA) underwent shattering and splintering upon UV light exposure, the microplate counterparts displayed unique cracking patterns with fissures yet retained their overall structural integrity. In contrast, NA microrods underwent pronounced bending under identical irradiation conditions. These phenomena are attributed to the efficient lattice reconfiguration stemming from the [2 + 2] cycloaddition photochemical reaction within the crystals. An intermediate fluorescence enhancement was observed across all crystal types upon light exposure. Collectively, our results underscore the pivotal role of crystal shape in dictating photomechanical behavior, thereby heralding novel strategies for developing advanced photomechanical materials. Full article

The well-known effect of bending of acicular crystals undergoing photochemical reactions is associated with the transformation gradient across the crystal thickness caused by the absorption of light. It is believed that the direction of bending is unambiguously dictated by the sign of the axial component of the reaction strain and due to the higher light intensity on the irradiated side of the crystal. In this study, it is shown experimentally and theoretically that thin crystals with a convex irradiated surface bend in the opposite direction if their thickness is less than the light penetration depth. The reversal of the bending direction is due to the lens effect, able to overcome the absorption of light in a thin crystal and provide a higher light intensity on the rear side of the crystal. A crystal of [Co(NO₃)₅NO₂]Cl(NO₃) experiencing nitro-nitrito photoisomerization, begins to bend in the opposite direction after it is thinned by etching to 2 µm when irradiated at the wavelengths of 523 nm, 465 nm, and 403 nm, absorbed at a depth of more than 10 µm in the crystal, but bends in the normal direction under 350 nm light absorbed at a depth of about 1 µm. The experimental results are fully confirmed by modeling the interaction of plane EM wave with crystals of various cross sections. Full article

Photomechanical materials perform mechanical work in response to illumination. Photoisomerization-based photomechanical materials may operate in different regimes depending on the intensity of the illuminating light. We examine the photoresponse of liquid crystalline azo-acrylate networks and show that a material property, the characteristic intensity of the material, defines the boundaries between different regimes. Asymptotic analysis indicates that whereas at low relative light levels, photostress is proportional to intensity, at high levels, it is proportional to fluence. Model predictions are in good agreement with the experimental results. Full article

9-Methylanthracene (9MA) undergoes a concerted [4 + 4] photodimerization in its crystal form that can be harnessed in order to generate photomechanical motions such as bending, twisting, and expansion. As described in this paper, 9MA nanowires were grown in anodic aluminum oxide (AAO) templates with the goal of using the crystal expansion to generate a net increase in the height of the composite disk. The growth conditions were optimized in order to raise the filling amount from 28% to 77% of the available volume in the porous AAO. A new experimental method for detecting motion, based on the analysis of data from a dynamically misaligned Michelson interferometer, was developed. Template bending was observed, showing that the photodimerization of the confined nanowires generated mechanical work, but no conclusive evidence for surface disruption or vertical translation was observed. Optical measurements, as well as atomic force and scanning electron microscopy, showed that incomplete filling, crystal orientation, and debris from template polishing likely prevented the observation of vertical actuation in these nanocrystal composites. This work highlights some of the practical challenges that are involved in creating photomechanical actuators using the organic–inorganic composite approach, with the two most significant being (1) the uniform filling of the porous template with the organic active material and (2) the removal of excess organic material from the template’s surface. Full article

The initial processes of the phase transition dynamics of liquid crystals (LCs) subject to UV pulse irradiation were clarified using a nanosecond time-resolved imaging technique called pattern-illumination time-resolved phase microscopy (PI-PM). Two types of LCs were studied: a photo-responsive LC and dye-doped LCs. We found two steps of molecular disordering processes in the phase transition, namely local disordering proceeding anisotropically, followed by the spreading of the isotropic phase. These two processes were separated for a photo-responsive LC while being simultaneously observed for the dye-doped LCs. It was found that the photomechanical dyes induced the phase transition process faster than the photothermal dyes. Full article

Photomechanical materials exhibit mechanical motion in response to light as an external stimulus. They have attracted much attention because they can convert light energy directly to mechanical energy, and their motions can be controlled without any physical contact. This review paper introduces the photomechanical motions of photoresponsive molecular crystals, especially bending and twisting behaviors, from the viewpoint of symmetry breaking. The bending (right–left symmetry breaking) and twisting (chiral symmetry breaking) of photomechanical crystals are based on both intrinsic and extrinsic factors like molecular orientation in the crystal and illumination conditions. The ability to design and control this symmetry breaking will be vital for generating new science and new technological applications for organic crystalline materials. Full article

With continuous miniaturization of many technologies, robotics seems to be lagging behind. While the semiconductor technologies operate confidently at the nanometer scale and micro-mechanics of simple structures (MEMS) in micrometers, autonomous devices are struggling to break the centimeter barrier and have hardly colonized smaller scales. One way towards miniaturization of robots involves remotely powered, light-driven soft mechanisms based on photo-responsive materials, such as liquid crystal elastomers (LCEs). While several simple devices have been demonstrated with contracting, bending, twisting, or other, more complex LCE actuators, only their simple behavior in response to light has been studied. Here we characterize the photo-mechanical response of a linear light-driven LCE actuator by measuring its response to laser beams with varying power, pulse duration, pulse energy, and the energy spatial distribution. Light absorption decrease in the actuator over time is also measured. These results are at the foundation of further development of soft, light-driven miniature mechanisms and micro-robots. Full article

In this work, photomechanical molecular crystals of 4-(4-(6-Hydroxyhexyloxy) phenylazo) pyridine (6cazpy) and its zinc(II) organic complex (complex-I) were synthesized and crystallized. DSC and TGA were used to characterize and compare properties of 6cazpy and its complex-I crystals. Photoinduced motions of 6cazpy crystals and its complex-I crystals were investigated and compared by UV/Vis irradiation. Bending away motions from the light source were observed from both 6cazpy crystals and its complex-I crystals. The bending away motion was attributed to the trans-to-cis photoisomerization of azopyridine derivatives in the crystalline phase. It is worth noting that the photomechanical properties of complex-I were enhanced by the formation of the ligand, which might be caused by the looser packing of molecules inside complex-I crystal. In addition, because of the existence of ligand, which combined two photoactive groups in each complex-I molecule, the isomerization reactions of these two photoactive groups in the molecules can increase the photomechanical movement ability of the crystal. It was also found that the crystal size and shape will affect the photoinduced movement of the crystals. PXRD and AFM were used to investigate the molecular mechanism and the surface topological change upon photoisomerization. The corresponding mechanism was proposed. Full article

Photomechanically responsive materials are promising candidates for future smart actuator applications. The photo-responsive behaviors originate from the photoisomerization of photochromic molecules. A typical photochromic compound, azobenzene, has been studied extensively in the solution state and has played a crucial role in the photomechanical behaviors of materials such as polymers and gels, via chemical bridging with their matrix. In contrast to polymers and gels, the photomechanical attributes of molecular crystals have not progressed to the same degree, due to their rigidity and fragility. However, the past decade has witnessed an increasing number of reports of the photomechanical motion of molecular crystals, including azobenzene crystals. This paper reviews the current state-of-the-art of mechanically responsive azobenzene crystals, including the history, crystal design strategy, and future promising applications. Full article

We investigated photoinduced crystal bending behavior of various photochromic diarylethenes. In all the diarylethene derivatives we used in this work, the relationship between the initial photoinduced bending speed and the crystal thickness was well explained by the easy-handled Timoshenkoʼs bimetal model. Moreover, we proposed a quantitative analysis method to reveal the relationship between the bending speed and the molecular structure of diarylethenes. These results provide the quantitative evaluation method of the photoinduced crystal bending speed. Full article

Optically directed shape adaptive responses have been sought after for many decades in photoresponsive polymeric materials. A number of recent examinations have elucidated elucidated the unique opportunities of photomechanical responses realized in azobenzene-functionalized liquid crystalline polymer networks (both elastomers and glasses). This work summarizes and contrasts the photomechanical response of glassy polydomain, monodomain, and twisted nematic azo-LCN materials to blue-green irradiation. Building from this summary, the combinatorial photomechanical response observed upon irradiation of composite cantilevers is examined. Large scale shape adaptations are realized, with novel responses that may be of potential use in future employment of these materials in actuation. Full article