Latest ArticlesEnaminones, which possesses both the nucleophilic enamine as well as electrophilic enone structures, are well known versatile building blocks in organic synthesis. Meanwhile, visible light-mediated reactions have emerged as useful synthetic strategy with enhanced sustainability. Around the last decade, various photochemical transformations of enaminones have been developed to construct cyclic or acyclic compounds. In this review, we describe the recent advances in visible light-mediated chemical transformations of enaminones. Detailed discussion on the reaction mechanism of the related reactions is given to provide guide to the reader. Finally, a summary on the existing challenges and the future outlook towards the development of practical photocatalytic reactions of enaminones is also presented.
Lithium (Li) dendrite issue, which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase (SEI), impedes the further development of high-energy Li metal batteries. However, the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short. Herein, we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix. The generated Co and LiF both enable fast Li-ion diffusion kinetics, meanwhile, the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites, thereby contributing to uniform Li nucleation and non-dendritic growth. As a result, a dendrite-free Li deposition with a low overpotential (16.1 mV) is achieved, which enables an extended lifespan over 750 h under strict conditions. The full cells with high-mass-loading LiFePO4 (11.5 mg/cm2) as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4% after undergoing 180 cycles.
Nitrate (NO3−) electroreduction reaction (NO3−RR) provides an attractive and sustainable route for NO3− pollution mitigation or energy-saved ammonia (NH3) synthesis. In this work, high-quality B and Fe co-doped Co2P hollow nanocubes (B/Fe-Co2P HNCs) are successfully synthesized though simultaneous boronation-phosphorization treatment, which reveal outstanding selectivity, activity, stability for the NO3− to NH3 conversion in neutral electrolyte because of big surface area, fast mass transport, superhydrophilic surface, and optimized electronic structure. B/Fe-Co2P HNCs can achieve the high NH3 yield rate (22.67 mg h−1 mgcat−1) as well as Faradaic efficiency (97.54%) for NO3−RR, greatly outperforming most of non-precious metal based NO3−RR electrocatalysts.
In recent years, due to the increasing demand for portable electronic devices, rechargeable solid-state battery technology has developed rapidly. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. Therefore, a better understanding of the relationship between electrochemical mechanism and structural properties from theory and experiment will enable us to accelerate the development of high-performance and security batteries. This review discusses the interplay between theoretical calculation and experiment in the study of lithium ion battery materials. We introduce the application of theoretical calculation method in solid-state batteries through the combination of theory and experiment. We present the concept and assembly technology of solid-state batteries are reviewed. The basic parameters of solid-state electrolytes, especially sulfide-based solid-state electrolytes and their interface mechanisms with high-voltage cathode materials, are analyzed by theoretical methods. We present an overview on the scientific challenges, fundamental mechanisms, and design strategies for solid-state batteries, especially focusing on the issues of stability on solid-state electrolytes and the associated interfaces with both cathode and electrolyte. Owing to the theoretical models, we can not only reveal the unprecedented mechanism from the atomic scale, but also analyze the interface problems in the battery thoroughly, thus effectively designing more promising electrolyte and interface coating materials. It blazed a new trial for engineering an interphase with improved interfacial compatibility for a long-term cyclability.
Functional materials with multiple properties are urgent to be explored to reach high requirements for applications nowadays. In this work, a new multifunctional one-dimensional (1D) chain compound [N(C3H7)4][Cu(ohpma)]·H2O 1 (ohpma = deprotonated N-(2-hydoxyphenyl)oxamic acid) exhibiting both 1D antiferromagnetic and nonlinear optical properties, which are both originated from the same polar [Cu(C8H4NO4)] magnetic units, has been successfully synthesized by evaporation at room temperature. Bis-polydentate nature of the (ohpma)3− ligand with constrained tridentate and bidentate coordination sites conducts Cu2+ ions coordinating in different geometries and forms 1D chains along the c axis, which are further separated by the [N(C3H7)4]+ cations. And the 1D magnetic chains further exhibit noncentrosymmetric polar arrangement. Nonlinear optical study shows polar compound 1 exhibits a discernible second-harmonic generation (SHG) efficiency and the calculation of the partial density of states indicates that the SHG efficiency of 1 is mainly originated from the polar [Cu(C8H4NO4)] magnetic units. Moreover, magnetic susceptibility shows a broad maximum around 70 K with strong intrachain interaction of J/kB = −113.0 K but no long-range order is observed down to 2 K, suggesting that 1 shows a good 1D magnetism. Both good 1D magnetism and SHG activity suggest that 1 could be as a potential multifunctional material, particularly.
Cyclic polymers are a class of polymers that feature endless topology, and the synthesis of cyclic polymers has attracted the attention of many researchers. Herein, cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations. Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)) (P(OEGA-co-DDA)) precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using a bifunctional chain transfer agent with two anthryl end groups. The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water. By irradiating the aqueous solution of the nanoparticles with 365 nm UV light, cyclic polymers were synthesized successfully via coupling of anthryl groups. The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA) copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via 1H nuclear magnetic resonance (1H NMR), dynamic light scattering (DLS), UV‒visible (vis) analysis, three-detection size exclusion chromatography (TD-SEC) and transmission electron microscopy (TEM). It was found that by adjusting the content of the hydrophilic segments in linear precursors, single chain polymeric nanoparticles (SCPNs) can be generated at high polymer concentrations. Therefore, cyclic polymers with high purity can be constructed efficiently. This method overcomes the limitation of traditional ring-closure method, which is typically conducted in highly dilute conditions, providing an efficient method for the scalable preparation of cyclic polymers.
Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities. However, it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure. In this review, research progress in the development of porphyrin-based saccharide sensors is described with representative examples. We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability, long emission wavelength, and multiple structural modification strategies. Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules. In the first section, recognition unit, design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed. While in the second section, development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized. Looking through the design strategy and sensing performance of reported achievements, it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.
The preparation of medium-sized benzo[b]azocines has always been challenging because of inherently unfavorable enthalpy and entropy factors. This report presents a novel approach for accessing 8-membered seleno-benzo[b]azocines via electrochemically-driven seleno-cyclization. This method enables room-temperature preparation of various structurally diverse medium-sized seleno-benzo[b]azocines. The facile deselenation of the seleno-cyclization products to generate functionalized dienes is an additional benefit of this indispensable reaction. Mechanistic insights are presented based on radical inhibition experiments and cyclic voltammetry measurements, which elucidate the radical pathway. Finally, density functional theory calculations further rationalize the rate-determining step and the unique chemoselectivity observed in this transformation.
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities, such as free carboxylic acid, aldehyde, halogen (including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp3)–H bonds, and short-lived reactive intermediates (aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode (BUME) with nano-electrospray ionization mass spectrometry.
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