Photomechanical Materials Research Articles

The Use of Photocycloaddition Reactions to Drive Mechanical Motions Resembling Humanoid Movements

AbstractWith the aim of producing a photomechanical material for incorporation in soft microrobots, a one‐dimensional diene coordination polymer (CP) [Cd(F‐bpeb)(3‐CBA)2]n (CP1, F‐bpeb=4,4′‐((1E,1′E)‐(2,5‐difluoro‐1,4‐phenylene)bis(ethene‐2,1‐diyl))dipyridine, 3‐HCBA=3‐chlorobenzoic acid) was synthesized and characterized. Irradiation of CP1 with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting in the introduction of crystal strain which triggers various types of crystal movements. Composite films of CP1‐PVA (SC) fabricated by dispersing CP1 crystals into polyvinyl alcohol (PVA) solution allow amplification of the crystal movement so that the film strips exhibit fast and flexible curling upon photoirradiation. The composite films may be cut into long rectangular strips and folded to simulate soft microrobots which exhibit a variety of fast, flexible and continuous photomechanical movements resembling a human performing various gymnastic exercises.

Shape Dependence of Photoresponsive Molecular Crystals Composed of Naphthyl Acrylic Acid Stimulated by Solid-State [2 + 2] Photocycloaddition

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.

Highly Twisted Azobenzene Ligand Causes Crystals to Continuously Roll in Sunlight.

Direct conversion of solar energy to mechanical work promises higher efficiency than multistep processes, adding a key tool to the arsenal of energy solutions necessary for our global future. The ideal photomechanical material would convert sunlight into mechanical motion rapidly, without attrition, and proportionally to the stimulus. We describe crystals of a tetrahedral isocyanoazobenzene-copper complex that roll continuously when irradiated with broad spectrum white light, including sunlight. The rolling results from bending and straightening of the crystal due to blue light-driven isomerization of a highly twisted azobenzene ligand. These findings introduce geometrically constrained crystal packing as a strategy for manipulating the electronic properties of chromophores. Furthermore, the continuous, solar-driven motion of the crystals demonstrates direct conversion of solar energy to continuous physical motion using easily accessed molecular systems.

Regimes in the Response of Photomechanical Materials

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.

Analysis of molecular photomechanical performance using a one-dimensional harmonic model

The photochemical reaction of a molecule leads to a change in the position of its nuclei that can be harnessed to perform mechanical work. Photomechanical materials use this effect to act as light-powered actuators. In this paper, a one-dimensional model based on coupled harmonic potential energy surfaces is developed to describe the photomechanical response of a molecule. This model generates predictions that are qualitatively consistent with standard mechanochemistry models for ground state rate reactions. To analyze the photomechanical process, excited state dynamics like photon absorption and relaxation are included. The model allows us to derive analytical expressions for the work output, blocking force, and absorbed photon-to-work efficiency. The effects of nonadiabatic electronic coupling, unequal frequency potentials, and the cycling efficiency are also analyzed. If the starting state is the stable (lower energy) isomer, it is possible to attain photon-to-work efficiencies up to 55.4%. If initial state is higher in energy, for example a metastable isomer, then one-way efficiencies > 100% are possible due to the release of stored potential energy. Photomechanical materials can be competitive with photovoltaic–piezoelectric combinations in terms of efficiency, but current materials will require substantial improvement before they can approach the theoretical limits.Graphical abstract

Performance of Composite Glass-Diarylethene Crystal Photomechanical Actuator Membranes.

Hybrid organic-inorganic composites based on organic photochromic crystals embedded in inorganic templates provide a new approach to photomechanical materials. Diarylethene (DAE) nanowire crystals grown in Al2O3 membranes have exhibited reversible photoinduced bending and lifting [Dong, X., Chem. Mater. 2019, 31, 1016-1022]. In this paper, the hybrid approach is extended to porous SiO2 membranes. Despite the different template material (SiO2 instead of Al2O3) and much larger channels (5 μm diameter instead of 0.2 μm diameter), similar photomechanical behavior is observed for this new class of organic-inorganic hybrid actuators. The ability to reuse individual glass templates across different DAE filling cycles allows us to show that the DAE filling step is crucial for determining the mechanical work done by the bending template. The bending curvature also depends quadratically on the template thickness, in good agreement with theory. The light-induced bending can be repeated for up to 150 cycles without loss of performance, suggesting good fatigue resistance. The results in this paper demonstrate that the hybrid organic-inorganic approach can be extended to other host materials and template geometries. They also suggest that optimizing the organic filling and template thickness could improve the work output by an order of magnitude.

Photoreactive Crystals Exhibiting [2 + 2] Photocycloaddition Reaction and Dynamic Effects.

ConspectusConducting a reaction in the solid state eliminates the usage of solvents. If such reactions are conducted in a single-crystal to single-crystal (SCSC) fashion, then structural characterization by single-crystal X-ray crystallography (SCXRD) techniques provides unequivocal structural details. Although topochemical principles govern, getting single crystals at the end of a SCSC reaction purely depends on the experimental skills of the researchers. SCSC reactions are common among solid-state [2 + 2] cycloaddition reactions (hereafter "photoreaction") after the classical work of Schmidt and co-workers in 1960s. Synthons and tectons in the crystal engineering box can be exploited to bring the functional groups into the required alignment and packing to achieve the desired chemical reactivities and physical properties, respectively. Bringing a pair of alkenes closer together in the organic molecules provides an effective starting point to achieve the goal of crystal engineering.Further, understanding and controlling photoreactivity in the solid state provide a gateway to designing new advanced materials, for example, making cycloreversible optical storage materials, photosalient and photomechanical materials, highly crystalline or even single-crystalline organic polymers, covalent organic framework structures, and organic polymers incorporated inside metal-organic frameworks (MOFs). Photoreactions often proceed in a SCSC manner due to the limited movements of the closely disposed reactive functional groups in the crystals. Thus, these photoreactions yield not only quantitative photoproducts but also regio- and stereospecificity, which are otherwise inaccessible by solution syntheses.The traditional definition of crystals being hard, rigid, and brittle is no longer valid ever since the mechanically responsive crystals were discovered. These dynamic crystals undergo various movements like curling, jumping, hopping, popping, splitting, and wiggling, when exposed to light (called "photosalient effect") or heat (called "thermosalient" effect). These crystals generate new methods of transforming light and heat energy into mechanical work. Recently, photosalient behavior during the [2 + 2] cycloaddition reaction under UV light has been frequently observed. With the emergence of the field of "crystal adaptronics", dynamic photoreactive crystals have emerged as smart actuating materials.This Account aims to provide an overview of the development in this area, since it has garnered much attention among solid state chemists. While presenting selected examples of important strategies, we try to illustrate the intentions and concepts behind the methods developed, which will help in a rational approach for the fabrication of advanced solid state materials. Apart from topochemical transformations, the important roles played by weak interactions, guest solvents, and mechanical grinding have been highlighted in several classes of compounds to show structural transformations that defy the expected outcomes. Overall, the progress of [2 + 2] cycloaddition reaction in solid state materials has been discussed from UV induced structural transformations to the development of smart actuating materials.

Temperature-modulated photomechanical actuation of photoactive liquid crystal elastomers

Photoactive liquid crystal elastomers are polymer networks of liquid crystal mesogens embedded with chromophores like azobenzene. They undergo large deformation when illuminated by light of a certain wavelength through photochemical reaction, inspiring exciting new applications. However, despite the recent progresses in both the experiment and theory of these materials, the fundamental understanding of the temperature effect on their photomechanical actuation through various molecular-to-mesoscale processes have remained largely unexplored. This paper constructs a theoretical model to investigate this temperature-modulated photomechanical actuation, by integrating different temperature-dependent processes into a continuum framework. The model studies a special working condition where the material is subjected to a uniaxial tensile load, a prescribed temperature, and a polarized light illumination. We explore the free energy landscape of the system and the uniaxial stress–stretch responses under various conditions. We exploit the coupling between individual controls of temperature and light in a single photomechanical actuation for several working scenarios, including the temperature-modulated photomechanical snap-through instability, specific work, and blocking stress. We study the effect of the temperature-dependent backward isomerization of chromophores on the photomechanical actuation. These results are hoped to motivate future fundamental studies and new applications of various photomechanical material systems.

Inside Back Cover: Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9‐Methylanthracene Single Crystals (Angew. Chem. Int. Ed. 2/2022)

Photomechanical crystals composed of 9-methylanthracene molecules were investigated by Daichi Kitagawa, Christopher J. Bardeen, Seiya Kobatake, and co-workers in their Research Article (e202114089). The crystals that expand under illumination could potentially be used as photon-powered actuators. Moreover, the quantitative connection between molecular reaction kinetics and mechanical response in well-defined single crystals provides a new benchmark for analyzing these photomechanical materials.

Azobenzene‐Based Photomechanical Biomaterials

Biomaterials with stimuli sensitivity and good mechanical properties are garnering interest as an important branch of stimuli‐responsive materials. Among them, photomechanical biomaterials are an emerging class of eco‐friendly materials for the development of various biomedical devices because they offer high spatiotemporal control, on‐demand response, and noninvasive manipulation. In particular, azobenzene can be reversibly converted from the trans to the cis isomer under irradiation by different wavelengths of light. The significant changes in structural geometry and excellent fatigue resistance of azobenzene upon isomerization allow its use in the fabrication of materials with photoresponsive properties, such as bending, twisting, coiling, buckling, expansion, or even jumping. However, studies on the photomodulated mechanical performance of azobenzene‐based bulk biomaterials have rarely been reported. This review focuses on the photomechanical effects that occur in various systems incorporated with azobenzene moieties. Within this framework, the advantages of azobenzene in different photomechanical materials, including liquid crystals, bulk films, gels, and bulk fibers, are discussed. In each section, the light‐induced modulation of mechanical properties, including tensile strength, modulus, and toughness, is highlighted. Finally, a summary and outlook for the development of azobenzene‐based photomechanical materials is presented.

Light-induced stress and work in photomechanical materials.

Increasingly important photomechanical materials produce stress and mechanical work when illuminated. We propose experimentally accessible performance metrics for photostress and photowork, enabling comparison of materials performance. We relate these metrics to material properties, providing a framework for the design and optimization of photomechanical materials.

Bridging photochemistry and photomechanics with NMR crystallography: the molecular basis for the macroscopic expansion of an anthracene ester nanorod.

Crystals composed of photoreactive molecules represent a new class of photomechanical materials with the potential to generate large forces on fast timescales. An example is the photodimerization of 9-tert-butyl-anthracene ester (9TBAE) in molecular crystal nanorods that leads to an average elongation of 8%. Previous work showed that this expansion results from the formation of a metastable crystalline product. In this article, it is shown how a novel combination of ensemble oriented-crystal solid-state NMR, X-ray diffraction, and first principles computational modeling can be used to establish the absolute unit cell orientations relative to the shape change, revealing the atomic-resolution mechanism for the photomechanical response and enabling the construction of a model that predicts an elongation of 7.4%, in good agreement with the experimental value. According to this model, the nanorod expansion does not result from an overall change in the volume of the unit cell, but rather from an anisotropic rearrangement of the molecular contents. The ability to understand quantitatively how molecular-level photochemistry generates mechanical displacements allows us to predict that the expansion could be tuned from +9% to −9.5% by controlling the initial orientation of the unit cell with respect to the nanorod axis. This application of NMR-assisted crystallography provides a new tool capable of tying the atomic-level structural rearrangement of the reacting molecular species to the mechanical response of a nanostructured sample.

Photomechanical materials and applications: a tutorial

The transistor has revolutionized civilization. The photon will enable the next revolution provided that photomechanical materials, which convert light energy into mechanical work, can be made substantially more efficient. This tutorial develops a unified picture of the photomechanical response from its microscopic origins to the bulk response. A statistical model of the relationship between the photomorphon, the smallest photomechanical material unit, and the bulk response provides the context for understanding the various mechanisms that can contribute. We then present experimental details of how the photomechanical response is measured and used to deduce the underlying mechanisms. A figure of merit for the photomechanical efficiency is defined and materials are reviewed. Finally, we describe the photomechanical optical device (POD) and how PODs can be combined to form highly intelligent materials. This tutorial spans the multidisciplinary topics needed to (1) understand the fundamental physics of the response, (2) design and process materials to control the response, and (3) build new devices and integrated photomechanical systems.

Symmetry Breaking and Photomechanical Behavior of Photochromic Organic Crystals

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.

Mechanical Properties and Photomechanical Fatigue of Macro- and Nanodimensional Diarylethene Molecular Crystals.

The diarylethene derivative, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene, undergoes a reversible photoisomerization between its ring-open and ring-closed forms in the solid-state and has applications as a photomechanical material. Mechanical properties of macrocrystals, nanowire single crystals, and amorphous films as a function of multiple sequential UV and visible light exposures have been quantified using atomic force microscopy nanoindentation. The isomerization reaction has no effect on the elastic modulus of each solid. But going from the macro- to the nanowire crystal results in a remarkable over 3-fold decrease in the elastic modulus. The macrocrystal and amorphous solids are highly resistant to photomechanical fatigue, while nanowire crystals show clear evidence of photomechanical fatigue attributed to a transition from crystal to amorphous forms. This study provides first experimental evidence of size-dependent photomechanical fatigue in photoreactive molecular crystalline solids and suggests crystal morphology and size must be considered for future photomechanical applications.

Photomechanical materials driven by photoisomerization or photodimerization

Light is an adjustable, multiparameter stimulus that can be used for fine, noncontact manipulation or as an energy supply. Recently, deformable light-controlled macroscopic materials have gained attention both from a fundamental research perspective and for various actuator applications. The main challenge in developing these materials is converting the photoinduced effects at the molecular level to macroscopic movements in the working pieces; a variety of mechanisms have been proposed for this. Both crystals and polymers containing photoreactive compounds have been intensively studied and have exhibited different advantages. Crosslinked liquid crystalline polymers have also attracted attention because they combine the advantages of macroscopically deformable polymers and crystals. In most circumstances, photodeformable materials contain photoreactive molecules that absorb light of a specific wavelength and thus undergo structural changes. This is followed by concomitant changes in their physical and chemical properties, resulting in macroscopic mechanical movements. Therefore, various photoreactions have been studied to induce macroscopic deformations using light. The purpose of this review is to highlight key examples in the design of photodeformable materials using various photoreactions and to introduce some new and evolving trends by highlighting recent research. Macroscopic deformable materials controlled by light have been the subject of growing research interest in the last few decades due to both their fundamental properties and their wide applicability. In this review, examples of photomechanical effects in crystals, polymers, and CLCPs based on photoisomerization and photodimerization are reviewed.

A nonlinear beam model of photomotile structures.

Actuation remains a significant challenge in soft robotics. Actuation by light has important advantages: Objects can be actuated from a distance, distinct frequencies can be used to actuate and control distinct modes with minimal interference, and significant power can be transmitted over long distances through corrosion-free, lightweight fiber optic cables. Photochemical processes that directly convert photons to configurational changes are particularly attractive for actuation. Various works have reported light-induced actuation with liquid crystal elastomers combined with azobenzene photochromes. We present a simple modeling framework and a series of examples that study actuation by light. Of particular interest is the generation of cyclic or periodic motion under steady illumination. We show that this emerges as a result of a coupling between light absorption and deformation. As the structure absorbs light and deforms, the conditions of illumination change, and this, in turn, changes the nature of further deformation. This coupling can be exploited in either closed structures or with structural instabilities to generate cyclic motion.

Inorganic–Organic Hybrid Photomechanical Crystals of Azobenzene-modified Polyhedral Oligomeric Silsesquioxane (POSS)

A new class of inorganic–organic hybrid photomechanical material has been created by mono-substitution of polyhedral oligomeric silsesquioxane (POSS) with an azobenzene group via amide bond formation. This compound formed needle-like molecular crystals showing reversible photoinduced bending motions. This finding provides a new design concept of photomechanical materials for various applications.

Substituent Effect on Triplet State Aromaticity of Benzene.

Density functional theory calculations have been performed to explore the substituent effect on benzene's structure and aromaticity upon excitation to the first triplet excited state (T1). Discussion is based on spin density analysis, HOMA (harmonic oscillator model of aromaticity), NICS (nucleus-independent chemical shift), ACID (anisotropy of the induced current density), and monohydrogenation free energies and shows that a large span of aromatic properties, from highly antiaromatic to strongly aromatic, could be achieved by varying the substituent. This opens up a possibility of controlling benzene's physicochemical behavior in its excited state, while molecular motion, predicted for several derivatives, could be of interest for the development of photomechanical materials.

Using light intensity to control reaction kinetics and reversibility in photomechanical crystals.

4-Fluoro-9-anthracenecarboxylic acid (4F-9AC) is a thermally reversible (T-type) photomechanical molecular crystal. The photomechanical response is driven by a [4 + 4] photodimerization reaction, while the photodimer dissociation determines the reset time. In this paper, both the chemical kinetics of dimer dissociation (using a microscopic fluorescence-recovery-after-photobleaching experiment) and mechanical reset dynamics (by imaging bending microneedles) for single 4F-9AC crystals are measured. The dissociation kinetics depend strongly on the initial concentration of photodimer, slowing down and becoming nonexponential at high dimer concentrations. This dose-dependent behavior is also observed in the mechanical response of bending microneedles. A new feature in the photomechanical behavior is identified: the ability of a very weak control beam to suppress dimer dissociation after large initial dimer conversions. This phenomenon provides a way to optically control the mechanical response of this photomechanical crystal. To gain physical insight into the origin of the nonexponential recovery curves, the experimental results are analyzed in terms of a standard first-order kinetic model and a nonlinear Finke–Watzky (FW) model. The FW model can qualitatively reproduce the transition from exponential to sigmoidal recovery with larger initial conversions, but neither model can reproduce the suppression of the recovery in the presence of a weak holding beam. These results highlight the need for more sophisticated theories to describe cooperative phenomena in solid-state crystalline reactions, as well as demonstrating how this behavior could lead to new properties and/or improved performance in photomechanical materials.