Heat-Set Supramolecular Hydrogelation by Regulating the Hydrophilic-Lipophilic Balance for a Tunable Circularly Polarized Luminescent Switch.

Heat-set supramolecular gels exhibited totally opposite phase behaviors of dissolution upon cooling and gelation on heating. They are commonly discovered by chance and their rational design remains a great challenge. Herein, a rational design strategy is proposed to realize heat-set supramolecular hydrogelation through regulation of the hydrophilic-lipophilic balance of the system. A newly synthesized amphiphile hydrogelator with pyrene embedded in its lipophilic terminal can self-assemble into a hydrogel through a heating and cooling cycle. However, the host-guest complex of the gelator and hydrophilic γ-cyclodextrin (γ-CyD) results in a sol at room temperature. Thus, heat-set hydrogelation is realized from the sol state in a controllable manner. Heat-set gelation mechanism is revealed by exploring critical heat-set supramolecular gelation and the related findings provide a general strategy for developing new functional molecular gels with tunable hydrophilic-lipophilic balance.

Spatially Confined Face-Selective Growth of Large-Area 2D Organic Molecular Crystals in a Supramolecular Gel for Highly Efficient Flexible Photodetection.

2D organic molecular crystals (2DOMCs) are promising materials for the fabrication of high-performance optoelectronic devices. However, the growth of organic molecules into 2DOMCs remains a challenge because of the difficulties in controlling their self-assembly with a preferential orientation in solution-process crystallization. Herein, fullerene is chosen as a model molecule to develop a supramolecular gel crystallization approach to grow large-area 2DOMCs by controlling the perfect arrangement on the {220} crystal plane with the assistance of a gelated solvent. In this case, the gel networks provide tuneable confined spaces to control the crystallization kinetics toward the growth of dominant crystal faces by their inhibiting motions of solvent or solute molecules to enable the growth of perfect crystals at appropriate nucleation rates. As a result, a large-area fullerene 2DOMC is produced successfully and its corresponding device on a flexible substrate exhibits excellent bendable properties and ultra-high weak light detection ability (2.9 × 1011 Jones) at a 10 V bias upon irradiation with 450 nm incident light. Moreover, its photoelectric properties remain unchanged after 200 cycles of bending at angles of 45, 90, and 180°. These results can be extended to the growth of other 2DOMCs for potentially fabricating advanced organic (opto)electronics.

An O-Carborane Derivative of Perylene Bisimide-Based Thin Film Displaying both Electrochromic and Electrofluorochromic Properties.

The widespread application in displays, information encryption, and sensors has boosted studies of electrochromic (EC) systems combining large contrast, fast response, high robustness, and low-cost properties. Herein, we report a film-type new EC system with a non-planar perylene bisimide-carborane derivative (PBI-CB) as the electroactive materials. It was revealed that the film demonstrated outstanding EC properties with response times of 1.18 and 0.94 s for the coloration and bleaching processes, respectively, large transmittance variation around 630 nm (45.7%), and superior stability for more than 200 coloration-bleaching cycles. Moreover, the film also showed precious electrofluorochromic (EFC) properties. The emission around 650 nm at the "on" state could be more than 24.5 times than that at the "off" state, and the response times of the off and on processes could reach 2.2 s and 4.3 s, respectively. Considering the facts that the film was fabricated via simple drop-coating, the EC/EFC operation was performed via a routine three-electrode system and the voltage applied is only -1.3 V, we believe that the EC/EFC system as developed would find applications in smart windows, information encryption, optoelectrical sensing, etc. In addition, the work could also pave the way for developing combined EC/EFC systems via employing known organic fluorophores as the electrochemical active materials, which are not only abundant in numbers but also solution-processable.

High-Performance Sensing of Formic Acid Vapor Enabled by a Newly Developed Nanofilm-Based Fluorescent Sensor.

Although it is widely used in industry and food products, formic acid can be dangerous owing to its corrosive properties. Accurate determination of formic acid would not only benefit its qualified uses but also be an effective way to avoid corrosion or injury from inhalation, swallowing, or touching. Herein, we present a nanofilm-based fluorescent sensor for formic acid vapor detection with a wide response range, fast response speed, and high sensitivity and selectivity. The nanofilm was synthesized at a humid air/dimethyl sulfoxide (DMSO) interface through dynamic covalent condensation between two typically designed building blocks, de-tert-butyl calix[4]arene-tetrahydrazide (CATH) and 4,4',4″,4‴-(ethene-1,1,2,2-tetrayl)tetra-benzaldehyde (ETBA). The as-prepared nanofilm is uniform, flexible, fluorescent, and photochemically stable. The thickness and fluorescence intensity of the nanofilm can be facilely adjusted by varying the concentration of the building blocks and the sensing performance of the nanofilm can be optimized accordingly. Based on the nanofilm, a fluorescent sensor with a wide response range (4.4 ppt-4400 ppm) for real-time and online detection of formic acid vapor was built. With the sensor, a trace amount (0.01%) of formic acid in petroleum ether (60-90 °C) can be detected within 3 s. Besides, fluorescence quenching of the nanofilm by formic acid vapor can be visualized. It is believed that the sensor based on the nanofilm would find real-life applications in corrosion and injury prevention from formic acid.

High-Performance Ketone Sensing in Vapor Phase Enabled by o-Carborane-Modified Cyclometalated Alkynyl-Gold(III) Complex-Based Fluorescent Films.

Development of high-performance, low-power-consumption, small-sized detectors is a key issue for fabricating specific miniaturized chromatographs (GCs). Herein, we report, for the first-time, utilization of a film-based fluorescent sensor as a GC detector. In the studies, we designed a new o-carborane derivative of a known cyclometalated alkynyl-gold(III) complex, Au-CB. Unlike the parent gold(III) complex, the newly synthesized Au-CB depicted a remarkable aggregation-induced emission (AIE) property, enabling fabrication of a fluorescent film. The film emission is highly sensitive to the presence of ketones such as acetone, 2-pentanone, 3-pentanone, cyclopentanone, etc., in the air. It was demonstrated that the sensing performance of the film could be further improved by changing the film from a planar structure to a tubular one. Via combination with an earlier reported homemade sensory device, a conceptual film-based fluorescent sensor was developed, which demonstrated instant and fully reversible response to the ketones. The experimental detection limits for cyclohexanone and acetone could be lower than 0.08 and 13.0 ppm, respectively. Moreover, the sensor is super stable, as 24 h continuous illumination resulted in less than 1.0% reduction of the fluorescence emission, 50 successive sensings showed no observable decay in the performance, and more than 1 year of storage had no effect upon the property. Further studies demonstrated that the film sensor could be used as a GC detector with performance comparable to the commercial flame ionization detector (FID), which lays the foundation for future applications in specific miniaturized GCs because of its merits in size, power consumption, carrier gas, etc.

Synthesis of Silica Microspheres-Inspired by the Formation of Ice Crystals-With High Homogeneous Particle Sizes and Their Applications in Photonic Crystals.

Silica microspheres (SMs) must possess the performances of desirable monodispersity, narrow particle size distribution, and high sphericity for preparing photonic crystals (PCs) and other materials such as microspheres reference material, etc. We have adopted the techniques of increasing reactant concentration and raising the temperature to improve the synthesis rate of SMs, gaining inspiration from the formation mechanism of ice crystals. SMs with uniform particle sizes (polydispersity index less than 0.05) and good spherical features were fabricated through homogeneous nucleation. The mathematical relationship between particle sizes of SMs and reactant concentrations is further fitted. High accuracy of the regression equation is verified by an F-test and verification experiment. Highly ordered PCs (the stacking fault is about 1.5%, and the point defect is about 10-3) with dense stacked opal structures have been obtained by self-assembly of SMs. In addition, highly ordered PCs (the stacking fault is about 3%, and the point defect is about 10-3) with non-dense packed opal structure and inverse opal structure were successfully prepared. PCs of inverse opal structure were used to examine their response characteristics to identify ethanol, exhibiting good performance. Our research may provide significant inspiration for the development of other sorts of microspheres.

A nanostructured Fc(COCH3)2 film prepared using silica monolayer colloidal crystal templates and its electrochromic properties.

Since oxidation and reduction reactions mainly take place on surfaces, enlarging the specific surface of redox materials is the key to achieving excellent electrochemical performance. In this work, by using silica monolayer colloidal crystal templates (MCCTs), a nanostructured Fc(COCH3)2 film is prepared successfully, and such a nanostructure could exhibit the following unique electrochemical properties: the MCCTs could impede the aggregation tendency of Fc(COCH3)2 and possess high electrochemical activity; Fc(COCH3)2 enlarges the contact area and offers more active sites and faster electronic transmission channels. The structure, optical and electrochemical properties of the nanostructured Fc(COCH3)2 were tested and then compared with those of compact Fc(COCH3)2 films to evaluate the role of the nanoarchitecture. The unique structure design of the Fc(COCH3)2 film enables outstanding performance, showing a large transmittance change (ΔT) of 37% at 550 nm when switched between 0.5 V and -2.5 V, which is approximately ninefold higher than that of the compact Fc(COCH3)2 film (approximately 4%). Response times of coloration and bleaching are found to be only 16.15 s and 5.56 s. Furthermore, the nanostructured Fc(COCH3)2 film shows much better cycling stability than the compact one. The results indicate that the nanostructure could significantly improve the electrochemical performance of the Fc(COCH3)2 film due to the increase in electrochemical active sites and the enhancement of the "D-to-A" redox switch of ferrocene.