Photo-actuators via epitaxial growth of microcrystal arrays in polymer membranes.

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).

Control of Photomechanical Crystal Twisting by Illumination Direction.

Photomechanical molecular crystals have been investigated as mesoscopic photoactuators. Here, we report how the photomechanical twisting of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a) crystals depends on illumination direction. The ribbon-like crystal of 1a could be successfully prepared by a sublimation method. The ribbon crystal exhibited reversible photomechanical crystal twisting upon alternating irradiation with ultraviolet (UV) and visible light. Moreover, changing the UV illumination direction with respect to the crystal resulted in different twisting modes, ranging from helicoid to cylindrical. Control of photomechanical crystal deformation by illumination direction provides a convenient and useful way to generate a variety of photomechanical motions from a single crystal.

Recent Advances of Nanomaterials-Based Molecularly Imprinted Electrochemical Sensors.

Molecularly imprinted polymer (MIP) is illustrated as an analogue of a natural biological antibody-antigen system. MIP is an appropriate substrate for electrochemical sensors owing to its binding sites, which match the functional groups and spatial structure of the target analytes. However, the irregular shapes and slow electron transfer rate of MIP limit the sensitivity and conductivity of electrochemical sensors. Nanomaterials, famous for their prominent electron transfer capacity and specific surface area, are increasingly employed in modifications of MIP sensors. Staying ahead of traditional electrochemical sensors, nanomaterials-based MIP sensors represent excellent sensing and recognition capability. This review intends to illustrate their advances over the past five years. Current limitations and development prospects are also discussed.

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.

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.

Characteristics of Hourly Extreme Precipitation along the Yangtze River Basin, China during Warm Season.

Based on the hourly gauge-satellite merged precipitation data with the spatial resolution of 0.1° × 0.1° during 2008-2016, the characteristics of extreme precipitation (EP) diurnal cycle along the Yangtze River Basin (YRB) and their regional and sub-seasonal differences during warm season have been indicated and revealed in this study. Results show that the EP amount (EPA) over most lower reaches of YRB exhibits two diurnal peaks with one in late afternoon and the other in morning, while the EPA over most eastern Tibetan Plateau (the Sichuan Basin and the northern Yunnan-Guizhou Plateau) generally peaks during late afternoon to midnight (midnight to early morning). The afternoon (morning) EPA diurnal peaks over the areas east to 110°E is mainly resulted from the short (long) duration EP events. However, both the short and long duration EP events lead to the nocturnal diurnal peaks and eastward propagating features of EPA over the regions west to110°E. The EP events over the Sichuan Basin generally begin at midnight and mostly peak around 03:00-04:00 Beijing time, and they start earlier and end later with the duration time increased. However, the EP events with short (long) duration over the lower reaches of YRB frequently start and peak in afternoon (early morning) and typically end at around 18:00 (07:00-08:00) Beijing time, and they start later (earlier) and end later with the duration time increased. Meanwhile, the EP frequency (EPF) diurnal cycles over the lower reaches of YRB exhibit obvious sub-seasonal differences in warm season, which show only a morning peak in the pre-Meiyu period, two comparable peaks with one in afternoon and the other in morning during the Meiyu period, and a predominant afternoon peak and a secondary morning peak in the post-Meiyu period, respectively. While the EPF over Sichuan Basin characterized by only one dominant early morning peak during all periods of the warm season exhibits much smaller sub-seasonal differences in the diurnal phase relative to that over the lower reaches of YRB.

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 motion of diarylethene molecular crystal nanowires.

Crystalline nanowires composed of the photochromic diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a) are prepared and characterized. 200 nanometer diameter wires with a length of 60 microns are grown by slow solvent annealing in a porous anodic aluminum oxide template. The nanowires are oriented crystals, as determined by X-ray diffraction measurements, and can be liberated by dissolving the template in acid. They exhibit pronounced bending when exposed to ultraviolet light that can be reversed by visible light irradiation. The bending-unbending sequence can be repeated for more than 10 cycles without fatigue. This robustness results from the ability of the nanowires to maintain their crystallinity during the forward and reverse reactions. The small diameter of these nanowires allows them to achieve curvatures that are at least 40 times greater (200 mm-1versus 5 mm-1) than those observed for micron-thick diarylethene needles. This first demonstration of photomechanical nanostructures based on diarylethene photochromism opens up the possibility of making more complicated structures composed of this high-performance photochrome.

Development of Spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene]-Based A-π-D-π-A Small Molecules with Different Acceptor Units for Efficient Organic Solar Cells.

Three acceptor-π-donor-π-acceptor (A-π-D-π-A) small molecules (STFYT, STFRDN, and STFRCN) with spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene] (STF) as the central donor unit, terthiophene as the π-conjugated bridge, indenedione, 3-ethylrhodanine, or 2-(1,1-dicyanomethylene)rhodanine as the acceptor unit are designed, synthesized, and characterized as electron donor materials in solution-processing organic solar cells (OSCs). The effects of the spiro STF-based central core and different acceptors on the molecular configuration, absorption properties, electronic energy levels, carrier transport properties, the morphology of active layers, and photovoltaic properties are investigated in detail. The three molecules exhibit desirable physicochemical features: wide absorption bands (300-850 nm) and high molar absorption coefficients (4.82 × 104 to 7.56 × 104 M-1 cm-1) and relatively low HOMO levels (-5.15 to -5.38 eV). Density functional theory calculations reveal that the spiro STF central core benefits to reduce the steric hindrance effect between the central donor block and terthiophene bridge and suppress excessive intermolecular aggregations. The optimized OSCs based on these molecules deliver power conversion efficiencies (PCEs) of 6.68%, 3.30%, and 4.33% for STFYT, STFRDN, and STFRCN, respectively. The higher PCE of STFYT-based OSCs should be ascribed to its better absorption ability, higher and balanced hole and electron mobilities, and superior active layer morphology as compared to the other two compounds. So far, this is the first example of developing the A-π-D-π-A type small molecules with a spiro central donor core for high-performance OSC applications. Meanwhile, these results demonstrate that using spiro central block to construct A-π-D-π-A molecule is an alternative and effective strategy for achieving high-performance small molecule donor materials.