Organic molecules that undergo supercooling can provide the basis for novel stimuli-responsive materials, but the number of such compounds is limited. Results in this paper show that the stable organic radical 2,2,6,6-tetramethyl-1-piperidine-1-oxyl (TEMPO) can form a stable supercooled liquid (SCL). Upon melting and cooling back to room temperature, the TEMPO SCL can persist for months, even after mild physical agitation. Its high vapor pressure can enable crystal growth at remote locations within the sample container over the course of days. Optical, electron paramagnetic resonance, and birefringence measurements show no evidence of new chemical species or partially ordered phases in the supercooled liquid. TEMPO's free radical character permits absorption of visible light that can drive photothermal melting to form the SCL, while a single nanosecond light pulse can initiate recrystallization of the SCL at some later time. This capability enables all-optical switching between the solid and the SCL phases. The physical origin of TEMPO's remarkable stability as an SCL remains an open question, but these results suggest that organic radicals comprise a new class of molecules that can form SCLs with potentially useful properties.
2-Azidoanthracene (2N3-AN) can act as a photochemical source of N2 gas when dissolved in an optically transparent polymer such as poly(methyl methacrylate) (PMMA). Irradiation at 365 or 405 nm of a 150 µm-thick polymer film submerged in water causes the rapid appearance of a surface layer of bubbles. The rapid appearance of surface bubbles cannot be explained by normal diffusion of N2 through the polymer and likely results from internal gas pressure buildup during the reaction. For an azide concentration of 0.1 M and a light intensity of 140 mW/cm2, the yield of gas bubbles is calculated to be approximately 40%. The dynamics of bubble growth depend on the surface morphology, light intensity, and 2N3-AN concentration. A combination of nanoscale surface roughness, high azide concentration, and high light intensity is required to attain the threshold N2 gas density necessary for rapid, high-yield bubble formation. The N2 bubbles adhered to the PMMA surface and survived for days under water. The ability to generate stable gas bubbles "on demand" using light permits the demonstration of photoinduced flotation and patterned bubble arrays.
Photomechanical crystals composed of three-dimensionally ordered and densely packed photochromes hold promise for high-performance photochemical actuators. However, bulk crystals with high structural ordering are severely limited in their flexibility, resulting in poor processibility and a tendency to fragment upon light exposure, while previous nano- or microcrystalline composites have lacked global alignment. Here we demonstrate a photon-fuelled macroscopic actuator consisting of diarylethene microcrystals in a polyethylene terephthalate host matrix. These microcrystals survive large deformations and show a high degree of three-dimensional ordering dictated by the anisotropic polyethylene terephthalate, which critically also has a similar stiffness. Overall, these ordered and compliant composites exhibit rapid response times, sustain a performance of over at least hundreds of cycles and generate work densities exceeding those of single crystals. Our composites represent the state-of-the-art for photochemical actuators and enable properties unattainable by single crystals, such as controllable, reversible and abrupt jumping (photosalient behaviour).
In the last century, molecular crystals functioned predominantly as a means for determining the molecular structures via X-ray diffraction, albeit as the century came to a close the response of molecular crystals to electric, magnetic, and light fields revealed that the physical properties of molecular crystals were as rich as the diversity of molecules themselves. In this century, the mechanical properties of molecular crystals have continued to enhance our understanding of the colligative responses of weakly bound molecules to internal frustration and applied forces. Here, the authors review the main themes of research that have developed in recent decades, prefaced by an overview of the particular considerations that distinguish molecular crystals from traditional materials such as metals and ceramics. Many molecular crystals will deform themselves as they grow under some conditions. Whether they respond to intrinsic stress or external forces or interactions among the fields of growing crystals remains an open question. Photoreactivity in single crystals has been a leading theme in organic solid-state chemistry; however, the focus of research has been traditionally on reaction stereo- and regio-specificity. However, as light-induced chemistry builds stress in crystals anisotropically, all types of motions can be actuated. The correlation between photochemistry and the responses of single crystals-jumping, twisting, fracturing, delaminating, rocking, and rolling-has become a well-defined field of research in its own right: photomechanics. The advancement of our understanding requires theoretical and high-performance computations. Computational crystallography not only supports interpretations of mechanical responses, but predicts the responses itself. This requires the engagement of classical force-field based molecular dynamics simulations, density functional theory-based approaches, and the use of machine learning to divine patterns to which algorithms can be better suited than people. The integration of mechanics with the transport of electrons and photons is considered for practical applications in flexible organic electronics and photonics. Dynamic crystals that respond rapidly and reversibly to heat and light can function as switches and actuators. Progress in identifying efficient shape-shifting crystals is also discussed. Finally, the importance of mechanical properties to milling and tableting of pharmaceuticals in an industry still dominated by active ingredients composed of small molecule crystals is reviewed. A dearth of data on the strength, hardness, Young's modulus, and fracture toughness of molecular crystals underscores the need for refinement of measurement techniques and conceptual tools. The need for benchmark data is emphasized throughout.
Photomechanical molecular crystals have garnered attention for their ability to transform light into mechanical work, but difficulties in characterizing the structural changes and mechanical responses experimentally have hindered the development of practical organic crystal engines. This study proposes a new computational framework for predicting the solid-state crystal-to-crystal photochemical transformations entirely from first principles, and it establishes a photomechanical engine cycle that quantifies the anisotropic mechanical performance resulting from the transformation. The approach relies on crystal structure prediction, solid-state topochemical principles, and high-quality electronic structure methods. After validating the framework on the well-studied [4 + 4] cycloadditions in 9-methyl anthracene and 9-tert-butyl anthracene ester, the experimentally-unknown solid-state transformation of 9-carboxylic acid anthracene is predicted for the first time. The results illustrate how the mechanical work is done by relaxation of the crystal lattice to accommodate the photoproduct, rather than by the photochemistry itself. The large â¼107 J m-3 work densities computed for all three systems highlight the promise of photomechanical crystal engines. This study demonstrates the importance of crystal packing in determining molecular crystal engine performance and provides tools and insights to design improved materials in silico.
Photoreactive molecular crystals have been intensively investigated as next-generation functional materials. Changes in physicochemical properties are usually interpreted in terms of static pre- and post-reaction molecular structures and packings determined by X-ray structure analysis. However, to elucidate the dynamic properties, it is necessary to understand the dynamic nature of photochemical kinetics in crystals. Reaction dynamics in the crystal phase can be dramatically different from those in dilute solution because the local molecular environment evolves as the surrounding reactant molecules are transformed into products. In this Review article, we summarize multiple examples of photochemical reactions in the crystalline phase that do not follow classical kinetic behavior. We also discuss different theoretical methods that can be used to describe this behavior. This Review article should help provide a foundation for future workers to understand and analyze photochemical reaction kinetics in crystals.
Lithography methods are commonly used to create structures in inorganic semiconductors like silicon but have not been widely applied to organic crystals. In this work, electron beam lithography (EBL) is used to pattern structures into single organic photomechanical crystals composed of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene. The electron beam creates amorphous regions of decomposed molecules, while the reactivity of the unexposed crystal regions is preserved under a removable Au coating. Exposure of the patterned crystal to 365 nm light causes ridges of amorphous material to increase in height by 30-70%. This height increase can be reversed by visible light exposure and undergo multiple cycles. The reversible surface morphology changes are strong enough to rupture a sheet of graphene placed on top of the patterned crystal. Surprisingly, the change in dimensions of the EBL features is an order of magnitude larger than the changes in overall crystal dimensions as deduced from X-ray diffraction experiments and microscopy observations. A dynamic extrusion model is presented to explain how nanoscale features imprinted into single crystals can amplify molecular-level photomechanical changes. This work demonstrates the capability of EBL methods to produce sub-micron structural features on single photomechanical crystals, providing a new route to monolithic light-powered actuator devices.
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.
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.
Photomechanical molecular crystals that expand under illumination could potentially be used as photon-powered actuators. In this study, we find that the use of high-quality single crystals of 9-methylanthracene (9MA) leads to more homogeneous reaction kinetics than that previously seen for polycrystalline samples, presumably due to a lower concentration of defects. Furthermore, simultaneous observation of absorbance and shape changes in single crystals revealed that the dimensional change mirrors the reaction progress, resulting in a smooth expansion of 7 % along the c-axis that is linearly correlated with reaction progress. The same expansion dynamics are highly reproducible across different single crystal samples. Organic single crystals exhibit well-defined linear expansions during 100 % photoconversion, suggesting that this class of solid-state phase change material could be used for actuation.
Organic phase change materials are used in actuators like wax motors. The solidâliquid phase transition that drives expansion is commonly induced by resistive heating that requires an electrical connection. The use of light to generate a phase change provides a non-contact way to power wax motors. Here, it is demonstrated that small molecules can act as absorbers to enable a photoinduced solidâliquid melting transition in eicosane, a low molecular weight phase change material. Three different small molecule absorbers are utilized: (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), azobenzene (AZOB), and guaiazulene (GAZ). The GAZ/eicosane mixture is characterized in detail because its absorption extends out to 750 nm, opening up the possibility of using near-infrared diodes as the photon source. The GAZ/eicosane composite is incorporated into a commercial wax motor assembly and 532 nm laser light is used to lift up to 400 g. The temporal response, work and force output, and efficiency are measured, and no loss of lifting capability or degradation is observed after ten cycles of irradiation. The incorporation of small aromatic molecules with low-energy absorption features into phase change materials can provide a general way to make light powered wax motors.
Phase Transition
Aluminum monochloride (AlCl) has been proposed as a promising candidate for laser cooling to ultracold temperatures, and recent spectroscopy results support this prediction. It is challenging to produce large numbers of AlCl molecules because it is a highly reactive open-shell molecule and must be generated in situ. Here we show that pulsed-laser ablation of stable, non-toxic mixtures of Al with alkali or alkaline earth chlorides, denoted XCln, can provide a robust and reliable source of cold AlCl molecules. Both the chemical identity of XCln and the Al : XCln molar ratio are varied, and the yield of AlCl is monitored using absorption spectroscopy in a cryogenic gas. For KCl, the production of Al and K atoms was also monitored. We model the AlCl production in the limits of nonequilibrium recombination dominated by first-encounter events. The non-equilibrium model is in agreement with the data and also reproduces the observed trend with different XCln precursors. We find that AlCl production is limited by the solid-state densities of Al and Cl atoms and the recondensation of Al atoms in the ablation plume. We suggest future directions for optimizing the production of cold AlCl molecules using laser ablation.
Covalent assemblies of conjugated organic chromophores provide the opportunity to engineer new excited states with novel properties. In this work, a newly developed triple-stranded cage architecture, in which meta-substituted aromatic caps serve as covalent linking groups that attach to both top and bottom of the conjugated molecule walls, is used to tune the properties of thiophene oligomer assemblies. Benzene-capped and triazine-capped 5,5'-(2,2-bithiophene)-containing arylene cages are synthesized and characterized using steady-state and time-resolved spectroscopic methods. The conformational freedom and electronic states are analyzed using time-dependent density functional theory. The benzene cap acts as a passive spacer whose electronic states do not mix with those of the chromophore walls. The excited state properties are dominated by through-space interactions between the chromophore subunits, generating a neutral Frenkel H-type exciton state. This excitonic state undergoes intersystem crossing on a 200 ps time scale while the fluorescence output is suppressed by a factor of 2 due to a decreased radiative rate. Switching to a triazine cap enables electron transfer from the chromophore-linker after the initial excitation to the exciton state, leading to the formation of a charge-transfer state within 10 ps. This state can avoid intersystem crossing and exhibits red-shifted fluorescence with enhanced quantum yield. The ability to interchange structural modules with different electronic properties while retaining the overall cage morphology provides a new approach for tuning the properties of discrete chromophore assemblies.
The fission of singlet excitons into triplet pairs in organic materials holds great technological promise, but the rational application of this phenomenon is hampered by a lack of understanding of its complex photophysics. Here, we use the controlled introduction of vacancies by means of spacer molecules in tetracene and pentacene thin films as a tuning parameter complementing experimental observables to identify the operating principles of different singlet fission pathways. Time-resolved spectroscopic measurements in combination with microscopic modelling enables us to demonstrate distinct scenarios, resulting from different singlet-to-triplet pair energy alignments. For pentacene, where fission is exothermic, coherent mixing between the photoexcited singlet and triplet-pair states is promoted by vibronic resonances, which drives the fission process with little sensitivity to the vacancy concentration. Such vibronic resonances do not occur for endothermic materials such as tetracene, for which we find fission to be fully incoherent; a process that is shown to slow down with increasing vacancy concentration.
Ruthenium-catalyzed butadiene-mediated benzannulation enabled the first synthesis of 3,10-(di-tert-butyl)rubicene and its N-doped derivatives as well as preliminary studies on their photophysical properties. Unlike the parent rubicene and 3,10-(di-tert-butyl)rubicene, which adopt classical herringbone-type packing motifs in the solid state, the N-doped congener 7 b displayed columnar packing with an alternating co-facial arrangement of aromatic and heteroaromatic substructures.
The ability to exhibit life-like oscillatory motion fueled by light represents a new capability for stimuli-responsive materials. Although this capability has been demonstrated in soft materials like polymers, it has never been observed in molecular crystals, which are not generally regarded as dynamic objects. In this work, it is shown that molecular crystalline microwires composed of (Z)-2-(3-(anthracen-9-yl)allylidene)malononitrile ((Z)-DVAM) can be continuously actuated when exposed to a combination of ultraviolet and visible light. The photo-induced motion mimics the oscillatory behavior of biological flagella and enables propagation of microwires across a surface and through liquids, with translational speeds up to 7â µm s-1 . This is the first example of molecular crystals that show complex oscillatory behavior under continuous irradiation. A model that relates the rotation of the transition dipole moment between reversible EâZ photoisomerization to the microscopic torque can qualitatively reproduce how the rotational frequency depends on light intensity and polarization.
Flagella/physiology , Heterocyclic Compounds/chemistry
The temperature-dependent fluorescence spectrum, decay rate, and spin quantum beats are examined in single tetracene crystals to gain insight into the mechanism of singlet fission. Over the temperature range of 250 K-500 K, the vibronic lineshape of the emission indicates that the singlet exciton becomes localized at 400 K. The fission process is insensitive to this localization and exhibits Arrhenius behavior with an activation energy of 550 ± 50 cm-1. The damping rate of the triplet pair spin quantum beats in the delayed fluorescence also exhibits an Arrhenius temperature dependence with an activation energy of 165 ± 70 cm-1. All the data for T > 250 K are consistent with direct production of a spatially separated 1(Tâ¯T) state via a thermally activated process, analogous to spontaneous parametric downconversion of photons. For temperatures in the range of 20 K-250 K, the singlet exciton continues to undergo a rapid decay on the order of 200 ps, leaving a red-shifted emission that decays on the order of 100 ns. At very long times (≈1 µs), a delayed fluorescence component corresponding to the original S1 state can still be resolved, unlike in polycrystalline films. A kinetic analysis shows that the redshifted emission seen at lower temperatures cannot be an intermediate in the triplet production. When considered in the context of other results, our data suggest that the production of triplets in tetracene for temperatures below 250 K is a complex process that is sensitive to the presence of structural defects.
Hollow organic molecular cocrystals comprised of 9-methylanthracene-1,2,4,5-tetracyanobenzene (9MA-TCNB) and naphthalene-1,2,4,5-tetracyanobenzene (NAPH-TCNB) were fabricated using a surfactant-mediated co-reprecipitation method. The crystals exhibit a narrow size distribution that can be easily tuned by varying the concentration of surfactant and incubation temperature. The rectangular crystals possess symmetrical twinned cavities with an estimated storage volume on the order of 10-10 â L. An aqueous dye solution can be incorporated into the cavities during crystal growth and stored inside for up to several hours, confirming the sealed nature of the hollow chambers. Our results demonstrate that it is possible to harness non-classical crystal growth to fabricate organic molecular crystals with novel topologies.
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.
