Thieno[3,2‐b]Thiophene End‐Capped all‐Sulfur Analog of 3,4‐Ethylenedioxythiophene and its Eletrosynthesized Polymer: Is Distorted Conformation Not Suitable for Electrochromism?

By employing planar thieno[3,2‐b]thiophene (TT) as end‐capped units and famous 3,4‐ethylenedioxythiophene (EDOT) or its all‐sulfur analog 3,4‐ethylenedithiathiophene (EDTT) as cores, two conjugated oligomer, TT‐EDOT‐TT and TT‐EDTT‐TT, have been synthesized and electropolymerized into electrochromic polymer films, P(TT‐EDOT‐TT) and P(TT‐EDTT‐TT), respectively. Due to strongly noncovalent inter/intramolecular interactions from S? S attraction of TT‐EDTT‐TT, it has twisted molecular configuration in contrast to planar TT‐EDOT‐TT. Spectroscopic, electrochemical, morphological as well as theoretical calculation studies of these oligomers or polymers were carried out to reveal the significant influence of such molecular geometry on their physicochemical and optoelectronic properties. According to electrochromic kinetics, P(TT‐EDTT‐TT) presented preferable electrochromic behavior such as the higher optical contrast (70.8%), favorable coloration efficiency (331.3 cm² C^?1) and fast response time (0.72 s). This research will help us deeply understand the effect of spatial organization of precursor molecules on the properties of electrochromic polymers and provides a promising strategy to develop high‐performance electrochromic materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1041–1048     

Salen–Mg-doped NH2–MIL-101(Cr) for effective CO2 adsorption under ambient conditions

A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH₂–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO₂ adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g⁻¹ for CO₂, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO₂ adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R²) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO₂/N₂ adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO₂ molecules.     

Effectively promoted catalytic activity by adjusting calcination temperature of Ce-Fe-Ox catalyst for NH3-SCR

A series of Ce-Fe-O_x catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NO_x by NH₃. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-O_x, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-O_x. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NO_x conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe³⁺ active species, higher Ce³⁺ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst.     

Generation and Propagation of Optical Superoscillatory Vortex Arrays

Superoscillation is an intriguing wave phenomenon which enables subwavelength features propagating into far field and hence has potential applications in super‐resolution microscopy as well as particle trapping and manipulation. While previous demonstrations mostly concentrate on designing complicated nanostructures for generating uncontrollable superoscillatory functions, here a new technique which allows for creating polynomially shaped superoscillatory functions that contain phase singularity arrays is demonstrated both theoretically and experimentally. Such a technique is implemented in optical experiments for the first time and controllable superoscillatory lobes with feature much below the diffraction limit is achieved. More importantly, a general theoretical framework, which, to our knowledge, has not been reported before, is developed to show how the created superoscillations propagate to a distance of many Rayleigh ranges and eventually disappear when the distance is sufficiently larger. The validity of the model is confirmed by the experiments. The results may trigger further studies in light field shaping and manipulations in subwavelength scale.     

3D Organic–Inorganic Perovskite Ferroelastic Materials with Two Ferroelastic Phases: [Et3P(CH2)2F][Mn(dca)3] and [Et3P(CH2)2Cl][Mn(dca)3]

Organic–inorganic hybrid perovskite-type multiferroics have attracted considerable research interest owing to their fundamental scientific significance and promising technological applications in sensors and multiple-state memories. The recent achievements with divalent metal dicyanamide compounds revealed such malleable frameworks as a unique platform for developing novel functional materials. Herein, two 3D organic–inorganic hybrid perovskites [Et₃P(CH₂)₂F][Mn(dca)₃] ( 1 ) and [Et₃P(CH₂)₂Cl][Mn(dca)₃] ( 2 ) (dca=dicyanamide, N(CN)₂⁻) are presented. Accompanying the sequential phase transitions, they display a broad range of intriguing physical properties, including above room temperature ferroelastic behavior, switchable dielectricity, and low-temperature antiferromagnetic ordering (T_c=2.4 K for both 1 and 2 ). It is also worth noting that the spontaneous strain value of 1 is far beyond that of 2 in the first ferroelastic phase, as a result of the precise halogen substitution. From the point view of molecular design, this work should inspire further exploration of multifunctional molecular materials with desirable properties.     

Design of and Stability Studies on Trefoil Knots Featuring RhCp* Building Blocks

Four flexible ligands with different lengths, degrees of flexibility, and steric bulk were synthesized and used to prepare metal-directed assemblies. Interestingly, minor differences among the ligands led to products with dramatically different topologies: a binuclear D -shaped macrocycle, tetranuclear rectangles, and hexanuclear trefoil knots. The interconversion of the trefoil-shaped complexes was also investigated. This contribution introduces a rare ligand-controlled trefoil–rectangle shape transformation in solution.     

Advantageous Interfacial Effects of AgPd/g-C3N4 for Photocatalytic Hydrogen Evolution: Electronic Structure and H2O Dissociation

Bimetallic AgPd nanoparticles have been synthesized before, but the interfacial electronic effects of AgPd on the photocatalytic performance have been investigated less. In this work, the results of hydrogen evolution suggest that the bimetallic AgPd/g-C₃N₄ sample has superior activity to Ag/g-C₃N₄ and Pd/g-C₃N₄ photocatalysts. The UV/Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, CO adsorption diffuse reflectance FTIR spectroscopy, and FTIR results demonstrate that in the AgPd/g-C₃N₄, the surface electronic structures of Pd and Ag are changed, which is beneficial for faster photogenerated electron transfer and greater H₂O molecule adsorption. In situ ESR spectra suggest that, under visible light irradiation, there is more H₂O dissociation to radical species on the AgPd/g-C₃N₄ photocatalyst. Furthermore, DFT calculations confirm the interfacial electronic effects of AgPd/g-C₃N₄, that is, Pd^δ−⋅⋅⋅Ag^δ+, and the activation energy of H₂O molecule dissociation on AgPd/g-C₃N₄ is the lowest, which is the main contributor to the enhanced photocatalytic H₂ evolution.