Search for: All records

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 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 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 7 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 E→Z photoisomerization to the microscopic torque can qualitatively reproduce how the rotational frequency depends on light intensity and polarization.

 

The molecule (E)‐(5‐(3‐anthracen‐9‐yl‐allylidene)‐2,2‐dimethyl‐[1,3] dioxane‐4,6‐dione) (E‐AYAD) undergoesE→Zphotoisomerization. In the solid state, this photoisomerization process can initiate a physical transformation of the crystal that is accompanied by a large volume expansion (ca. 10 times), loss of crystallinity, and growth of large pores. This physical change requires approximately 10 % conversion of theEisomer to theZisomer and results in a gel‐like solid with decreased stiffness that still retains its mechanical integrity. The induced porosity allows the expanding gel to engulf superparamagnetic nanoparticles from the surrounding liquid. The trapped superparamagnetic nanoparticles impart a magnetic susceptibility to the gel, allowing it to be moved by a magnetic field. The photoinduced phase transition, starting with a compact crystalline solid instead of a dilute solution, provides a new route for in situ production of functional porous materials.

 

9-Anthracene carboxylic acid derivatives comprise a family of thermally reversible photomechanical molecular crystals. The photomechanical response relies on a [4 + 4] photodimerization followed by dissociation that occurs on timescales of seconds to minutes. A combined theoretical and experimental investigation is undertaken to better understand how chemical modification of the anthracene core influences energetics of both the isolated molecule and the crystal lattice. We use both density functional theory and dispersion-corrected Moller–Plesset perturbation theory computational methods to establish orbital energies, photodimerization reaction energies, and lattice energies for a set of substituted 9-anthracene carboxylic acid molecules. The calculations reveal that steric interactions play a dominant role in the ability to form photodimers and indicate an energetic threshold of 80–90 kJ per mole for the dimerization reaction. Examination of intermolecular bonding in a subset of fluorinated 9ACs revealed the absence of H⋯F intermolecular bond formation and energy differences that can explain observed trends in the dissociation kinetics and mechanical reset times. Fluorescence recovery after photobleaching experiments shows that the photodimer dissociation kinetics depend on the amount of initial photodimer, preventing a straightforward correlation between halogen atom substitution and dissociation rates using the Bell–Evans–Polanyi principle. The results clarify how molecular structure affects intermolecular interactions and photoreactivity in this family of molecular crystals, but the origin of the complex photodimer dissociation dynamics remains an open question. 

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. 

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. 

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. 

( E )-4-Fluoro-cinnamaldehyde malononitrile (( E )- 4FCM ) is a new phenylbutadiene derivative that undergoes a [2+2] photocycloaddition in the crystal form. Optical absorption and proton nuclear magnetic resonance ( 1 H-NMR) measurements demonstrate that the solid-state ( E )- 4FCM photodimerization is a negative photochromic reaction that proceeds to 97% completion. The large geometry change and full conversion allow bulk crystals of ( E )- 4FCM to show strong photosalient effects when exposed to 405 nm ultraviolet light. When ( E )- 4FCM nanowires are grown in an anodic alumina oxide (AAO) template, they maintain a high degree of crystallinity and orientation, as determined by X-ray diffraction measurements. When illuminated, ( E )- 4FCM nanowire bundles exhibit a rapid expansion, during which they spread by as much as 300% in the lateral direction. This lateral expansion is at least partially due to a photoinduced crystal expansion along the diameter of the nanowires. When ( E )- 4FCM nanowires are confined inside the AAO template, the photoinduced expansion can be harnessed to deform the template, causing it to bend under UV light irradiation. The bending motion due to 2.0 mg of 4FCM in a template can cause the template to bend by up to 1.0 mm and lift up to 200 g. These results represent a significant improvement in work output relative to previous composite actuator membranes based on diarylethene photochromes. 

The photodegradation of avobenzone ( AV ), the only ultraviolet filter molecule approved by the Food and Drug Administration to absorb UVA radiation, is an important problem in sunscreen formulations. In this paper, the photophysics and photostability of AV in various solvent systems and in aqueous micelles are studied. AV in its keto–enol tautomer functions as an effective UVA protection agent. AV is highly susceptible to photoinduced diketonization in both nonpolar solvents and in aqueous aggregates but is considerably more stable in polar, protic solvents like methanol. By studying its stability in different surfactant solutions, we show that incorporation of AV into sodium dodecylsulfate (SDS) micelles can achieve stability levels comparable to neat methanol. Steady-state spectral shifts, fluorescence anisotropy, and time-resolved fluorescence decay measurements are all consistent with AV experiencing a polar environment after micellar encapsulation. It is proposed that AV is encapsulated in the palisade layer of the SDS micelles, which allows access to water molecules that facilitate the re-formation of the enol form after photon absorption and relaxation. Although the detailed mechanism of AV tautomerization remains unclear, this work suggests that tuning the chemical microenvironment of AV may be a useful strategy for improving sunscreen efficacy.