一例可分离的双核铁氢自由基阳离子

成功分离得到了一例双核铁氢自由基阳离子盐cis-[Fe₂Cp₂（μ-H）（μ-PPh₂）（CO）₂]^·+[Al（OC（CF₃）₃）₄]^-（cis-1^·+[Al（OC（CF₃）₃）₄]^-）晶体，并使用单晶X射线衍射、电子顺磁共振、红外光谱、紫外-可见光谱以及密度泛函理论对它进行了表征和理论计算。电子顺磁共振和密度泛函理论计算分析表明，自由基的自旋密度主要均等分布于2个铁原子上。     

Insights into dimethyl sulfoxide decomposition in Li-O2 battery: Understanding carbon dioxide evolution

DMSO has been widely investigated as a potential electrolyte for the Li-air battery systems, however its stability has been a topic of debate in the research community. In this communication we have identified the side reaction products during the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on Au in dimethyl sulfoxide-based electrolyte for Li-air battery by a combination of in-situ analytical tools: EQCM, SNIFTIRS, DEMS and XPS, in particular the evolution of CO₂ from the solvent decomposition.     

Potential Applications of Cucurbit[n]urils and Their Derivatives in the Capture of Hazardous Chemicals

Cucurbit[n]urils (Q[n]s) are a relatively young family of macrocycles, consisting of glycoluril units bridged by methylene groups, and their unique structures have attracted extensive attention from chemists in recent decades. Due to the presence of a rigid hydrophobic inner cavity and two polar outer portals lined with carbonyl groups, Q[n]s not only encapsulate guest species into the cavity, but also coordinate with metal ions/clusters. Considerable achievements have been obtained in the fields of Q[n]s-based host–guest chemistry, coordination chemistry, as well as the combination of host–guest and coordination chemistry. Furthermore, the outer surface of Q[n]s has been demonstrated to be capable of interacting with definite species to generate supramolecular architectures in recent years. With more in-depth research into Q[n]s, their application studies have also emerged as a hot topic. This Minireview focuses on recent advances in the potential applications of solid-state materials based on Q[n]s and their derivatives for the capture and adsorption of hazardous chemicals from a solution or a gas mixture.     

Thermo-induced structural transformation with synergistic optical and magnetic changes in ytterbium and erbium complexes

Dinuclear ytterbium and erbium based bifunction complexes Ln₂L₂(depma₂)Cl₂ (1-Ln, Ln = Yb and Er, H₂L = N¹,N³-bis(salicylideneimino)diethylenetriamine, depma₂ = dimerized 9-diethyl-phosphonomethylanthracene) are reported. They undergo thermo-induced consecutive phase transitions, first the dissociation of depma₂ ligand forming LnL(depma)Cl (2-Ln) and then the release of chloroethane forming LnL(epma) (3-Ln, epma = 9-ethylphosphonomethylanthrancene). The structural transformations are accompanied with synergetic switch of the luminescence in visible and NIR regions and also magnetic dynamics.     

The role of delay times in subcycle-resolved probe retardation measurements

The delay in the nonlinear response of matter to intense laser pulses has been studied since a long time regarding its nuclear contribution. In contrast, the electronic part of the nonlinear response in wide-band-gap dielectrics, which is usually dominant, is not well explored regarding its delay, and previous studies have revealed that the timescale is below 1 fs. Here, the influence of delay times on the recently introduced method of subcycle-resolved probe retardation measurements is investigated using a simulation. In the model assumed, the electronic nonlinearity is divided into the third order Kerr effect and the plasma contribution due to conduction band population in the strong laser field. In the regime of close-to-collinear pump-probe geometries, the probe retardation shows both π- and 2π-oscillations in the pump-probe delay. Sub-femtosecond delay times influence the phase of the oscillations significantly, but it remains difficult to distinguish the influence of the Kerr response from the plasma contribution.     

The fabrication of ReS2 flowers at controlled locations by chemical vapor deposition

Here we report a metal induced nucleation to realize the growth of ReS₂ flowers at controlled locations. The ordered arrays of ReS₂ flowers have been successfully prepared on SiO₂/Si substrate using Pt metal dots as nucleation sites and S, NH₄ReO₄ powders as precursors by a chemical vapor depostion method. The NH₄ReO₄ powders are used as the rhenium sources. The ReS₂ flowers are grown above the pre-patterned Pt dots, Raman and transmission electron microscopy measurements indicated that the prepared ReS₂ flowers have excellent crystalline quality.     

Vertically Grown Few-Layer MoS2 Nanosheets on Hierarchical Carbon Nanocages for Pseudocapacitive Lithium Storage with Ultrahigh-Rate Capability and Long-Term Recyclability

Molybdenum disulfide (MoS₂) is an intensively studied anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity, but it is still confronted by severe challenges of unsatisfactory rate capability and cycle life. Herein, few-layer MoS₂ nanosheets, vertically grown on hierarchical carbon nanocages (hCNC) by a facile hydrothermal method, introduce pseudocapacitive lithium storage owing to the highly exposed MoS₂ basal planes, enhanced conductivity, and facilitated electrolyte access arising from good hybridization with hCNC. Thus, the optimized MoS₂/hCNC exhibits reversible capacities of 1670 mAh g⁻¹ at 0.1 A g⁻¹ after 50 cycles, 621 mAh g⁻¹ at 5.0 A g⁻¹ after 500 cycles, and 196 mAh g⁻¹ at 50 A g⁻¹ after 2500 cycles, which are among the best for MoS₂-based anode materials. The specific power and specific energy, which can reach 16.1 kW and 252.8 Wh after 3000 cycles, respectively, indicate great potential in high-power and long-life LIBs. These findings suggest a promising strategy for exploring advanced anode materials with high reversible capacity, high-rate capability, and long-term recyclability.     

Visible-Light-Mediated Click Chemistry for Highly Regioselective Azide–Alkyne Cycloaddition by a Photoredox Electron-Transfer Strategy

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the Cu^I-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide–alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide–alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide–alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.     

CaPtAs: A new noncentrosymmetric superconductor

We report the discovery of a new noncentrosymmetric superconductor CaPtAs.It crystallizes in a tetragonal structure(space group I41md,No.109),featuring three dimensional honeycomb networks of Pt-As and a much elongated c-axis(a=b=4.18?,and c=43.70?).The superconductivity of CaPtAs with Tc=1.47 K was characterized by means of electrical resistivity,specific heat,and ac magnetic susceptibility.The electronic specific heat Ce(T)/T shows evidence for a deviation from the behavior of a conventional BCS superconductor,and can be reasonably fitted by a p-wave model.The upper critical fieldμ0Hc2 of CaPtAs exhibits a moderate anisotropy,with an in-plane value of around 204 mT and an out-of-plane value of 148 mT.Density functional theory calculations indicate that the Pt-5 d and As-4 p orbitals mainly contribute to the density of states near the Fermi level,showing that the Pt-As honeycomb networks may significantly influence the superconducting properties.