The 100 most-cited articles in Chemistry - A European Journal, 2024

Abstract The Fenton reaction refers to the reaction in which ferrous ions (Fe2+) produce hydroxyl radicals and other reactive oxidizing substances by decomposing hydrogen peroxide (H2O2). This paper reviews the mechanism, application system, and materials employed in the Fenton reaction including conventional homogeneous and non‐homogeneous Fenton reactions as well as photo‐, electrically‐, ultrasonically‐, and piezoelectrically‐triggered Fenton reactions, and summarizes the applications in the degradation of soil oil pollutions, landfill leachate, textile wastewater, and antibiotics from a practical point of view. The mineralization paths of typical pollutant are elucidated with relevant case studies. The paper concludes with a summary and outlook of the further development of Fenton‐like reactions.

Cancer, responsible for approximately 10 million lives annually, urgently requires innovative treatments, as well as solutions to mitigate the limitations of traditional chemotherapy, such as long-term adverse side effects and multidrug resistance. This review focuses on Carbon Dots (CDs), an emergent class of nanoparticles (NPs) with remarkable physicochemical and biological properties, and their burgeoning applications in bioimaging and as nanocarriers in drug delivery systems for cancer treatment. The review initiates with an overview of NPs as nanocarriers, followed by an in-depth look into the biological barriers that could affect their distribution, from barriers to administration, to intracellular trafficking. It further explores CDs' synthesis, including both bottom-up and top-down approaches, and their notable biocompatibility, supported by a selection of in vitro, in vivo, and ex vivo studies. Special attention is given to CDs' role in bioimaging, highlighting their optical properties. The discussion extends to their emerging significance as drug carriers, particularly in…

To tackle the global energy scarcity and environmental degradation, developing efficient electrocatalysts is essential for achieving sustainable hydrogen production via water splitting. Modulating the d-band center of transition metal electrocatalysts is an effective approach to regulate the adsorption energy of intermediates, alter reaction pathways, lower the energy barrier of the rate-determining step, and ultimately improve electrocatalytic water splitting performance. In this review, a comprehensive overview of the recent advancements in modulating the d-band center for enhanced electrocatalytic water splitting is offered. Initially, the basics of the d-band theory are discussed. Subsequently, recent modulation strategies that aim to boost electrocatalytic activity, with particular emphasis on the d-band center as a key indicator in water splitting are summarized. Lastly, the importance of regulating electrocatalytic activity through d-band center, along with the challenges and prospects for improving electrocatalytic water splitting performance by fine-tuning the transition…

The use of sulfonium salts in organic synthesis has experienced a dramatic increase during the last years that can arguably be attributed to three main factors; the development of more direct and efficient synthetic methods that make easily available sulfonium reagents of a wide structural variety, their intrinsic thermal stability, which facilitates their structural modification, handling and purification even on large scale, and the recognition that their reactivity resembles that of hypervalent iodine compounds and therefore, they can be used as replacement of such reagents for most of their uses. This renewed interest has led to the improvement of already existing reactions, as well as to the discovery of unprecedented transformations; in particular, by the implementation of photocatalytic protocols. This review aims to summarize the most recent advancements on the area focusing on the work published during and after 2020. The scope of the methods developed will be highlighted and their limitations critically evaluated.

Hydrogen may play a critical role in our efforts to de-carbonize by 2050. However, there remain technical challenges in the storage and transport of hydrogen. Metal-organic frameworks (MOFs) have shown significant promise for hydrogen storage at cryogenic temperatures. A material that can meet the US department of energy (DOE) ultimate goal of 6.5 wt. % for gravimetric performance and 50 g/L for volumetric storage at near-ambient temperatures would unlock hydrogen as a future fuel source for on-board applications. Metal-organic frameworks typically have low heat of adsorptions (i. e. 4-7 kJ/mol), whereas for storing significant quantities of hydrogen at near-ambient temperatures, 15-25 kJ/mol is likely required. In this review we explore the current methods used (i. e., open-metal sites, alkali dopants and hydrogen spillover) for promoting strong adsorption within MOFs. Further we discuss MOF-based materials with respect to the technical aspects of deliverable capacity, kinetics and stability.

Abstract Metal‐organic frameworks (MOFs) show potential application in many domains, in which photochromic MOFs (PMOFs) have received enormous attention. Researchers mainly utilize photoactive ligands to build PMOFs. Recently, the mixed electron donating and accepting ligands strategies have also been used to construct PMOFs driven by the electron transfer between nonphotochromic moieties. However, the potential interligand competition inhibits the formation of PMOFs. Therefore, the exploration of single‐ligand‐guided assembly is conductive for building PMOFs. Considering the existing electron accepting and donating role of pyridyl and carboxyl, the pyridinecarboxyate derived from the fusion of pyridyl and carboxyl units may serve as single ligand to yield PMOFs (Figure 1d). In this work, the coordination assembly of bipyridinedicarboxylate (2,2′‐bipyridine‐4,4′‐dicarboxylic acid, H 2 bpdc; 1,10‐phenanthroline‐2,9‐dicarboxylic acid, H 2 pda) and LaCl 3 generate two PMOFs, [La(bpdc)(H 2 O)Cl] ( 1 ) and [La(pda)(H 2 O) 2 Cl]⋅2H 2 O ( 2 ). Both complexes feature dinuclear lanthanum as…

In 1973, two major discoveries changed the face of selenium chemistry: the identification of the first mammal selenoenzyme, glutathione peroxidase 1, and the discovery of the synthetic utility of the so-called selenoxide elimination. While the chemical mechanism behind the catalytic activity of glutathione peroxidases appears to be mostly unveiled, little is known about the mechanisms of other selenoproteins and, for some of them, even the function lies in the dark. In chemistry, the capacity of organoselenides of catalyzing hydrogen peroxide activation for the practical manipulation of organic functional groups has been largely explored, and some mechanistic details have been clearly elucidated. As a paradox, despite the long-standing experience in the field, the nature of the active oxidant in various reactions still remains matter of debate. While many successes characterize these fields, the pharmacological use of organoselenides still lacks any true application, and while some organoselenides were found to be non-toxic and safe to use, to date no therapeutically approved use…

The environmental impact from the waste disposal has been widely concerned around the world. The conversion of wastes to useful resources is important for the sustainable society. As a typical family of wastes, biomass materials basically composed of collagen, protein and lignin are considered as useful resources for recycle and reuse. In recent years, the development of carbon material derived from biomasses, such as plants, crops, animals and their application in electrochemical energy storage have attracted extensive attention. Through the selection of the appropriate biomass, the optimization of the activation method and the control of the pyrolysis temperatures, carbon materials with desired features, such as high-specific surface area, variable porous framework, and controllable heteroatom-doping have been fabricated. Herein, this review summarized the preparation methods, morphologies, heteroatoms doping in the plant/animal-derived carbonaceous materials, and their application as electrode materials for secondary batteries and supercapacitors, and as electrode support for…

The difunctionalization of alkenes represents a powerful tool to incorporate two functional groups into the alkene bones for increasing molecular complexity and has been widely utilizations in chemical synthesis. Upon the catalysis of the green, sustainable, mild photo-/electrochemistry technologies, much attentions have been attracted to the development of new tactics for the transformations of the important alkene and alkane feedstocks driven by C-H radical functionalization. Herein, we summarize recent advances in the photo-/electrocatalytic difunctionalization of alkenes enabled by C-H radical functionalization. We detailedly discuss the substrate scope and the mechanisms of the photo-/electrocatalytic alkene difunctionalization reactions by selecting impressive synthetic examples, which are divided into four sections based on the final terminated step, including oxidative radical-polar crossover coupling, reductive radical-polar crossover coupling, radical-radical coupling, and transition-metal-catalyzed coupling.

Abstract Recent years have witnessed great research interests in developing high‐performance electrocatalysts for the two‐electron (2e − ) oxygen reduction reaction (ORR) that enables the sustainable and flexible synthesis of H 2 O 2 . Carbon‐based electrocatalysts exhibit attractive catalytic performance for the 2e − ORR, where oxygen‐containing functional groups (OFGs) play a decisive role. However, current understanding is far from adequate, and the contribution of OFGs to the catalytic performance remains controversial. Therefore, a critical overview on OFGs in carbon‐based electrocatalysts toward the 2e − ORR is highly desirable. Herein, we go over the methods for constructing OFGs in carbon including chemical oxidation, electrochemical oxidation, and precursor inheritance. Then we review the roles of OFGs in activating carbon toward the 2e − ORR, focusing on the intrinsic activity of different OFGs and the interplay between OFGs and metal species or defects. At last, we discuss the reasons for inconsistencies among different studies, and personal perspectives on the future…

Atomistic modeling can provide valuable insights into the design of novel heterogeneous catalysts as needed nowadays in the areas of, e. g., chemistry, materials science, and biology. Classical force fields and ab initio calculations have been widely adopted in molecular simulations. However, these methods usually suffer from the drawbacks of either low accuracy or high cost. Recently, the development of machine learning interatomic potentials (MLIPs) has become more and more popular as they can tackle the problems in question and can deliver rather accurate results at significantly lower computational cost. In this review, the atomistic modeling of catalytic systems with the aid of MLIPs is discussed, showcasing recently developed MLIP models and selected applications for the modeling of heterogeneous catalytic systems. We also highlight the best practices and challenges for MLIPs and give an outlook for future works on MLIPs in the field of heterogeneous catalysis.

Hydrogen-bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π-π stacking, highly interpenetrated networks, charge-assisted, ligand-bond-assisted, molecular weaving, and covalent cross-linking. Charge-assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge-assisted ionic…

Amyloid plaques are a major pathological hallmark involved in Alzheimer's disease and consist of deposits of the amyloid-β peptide (Aβ). The aggregation process of Aβ is highly complex, which leads to polymorphous aggregates with different structures. In addition to aberrant aggregation, Aβ oligomers can undergo liquid-liquid phase separation (LLPS) and form dynamic condensates. It has been hypothesized that these amyloid liquid droplets affect and modulate amyloid fibril formation. In this review, we briefly introduce the relationship between stress granules and amyloid protein aggregation that is associated with neurodegenerative diseases. Then we highlight the regulatory role of LLPS in Aβ aggregation and discuss the potential relationship between Aβ phase transition and aggregation. Furthermore, we summarize the current structures of Aβ oligomers and amyloid fibrils, which have been determined using nuclear magnetic resonance (NMR) and cryo-electron microscopy (cryo-EM). The structural variations of Aβ aggregates provide an explanation for the different levels of toxicity, shed…

In this review article, the synthesis, characterization and physico-chemical properties of the organic donor-acceptor complexes are highlighted and a special emphasis has been placed on developing them as semiconducting materials. The electron-rich molecules, i. e., donors have been broadly grouped in three categories, namely polycyclic aromatic hydrocarbons, nitrogen heterocycles and sulphur containing aromatic donors. The reactions of these classes of the donors with the acceptors, namely tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), tetracyanobenzene (TCNB), benzoquinone, pyromellitic dianhydride and pyromellitic diimides, fullerenes, phenazine, benzothiadiazole, naphthalimide, DMAD, maleic anhydride, viologens and naphthalene diimide are described. The potential applications of the resulting DA complexes for physico-electronic purposes are also included. The theoretical investigation of many of these products with a view to rationalise their observed physico-chemical properties is also discussed.

Abstract Overuse of fossil fuels and anthropogenic activities have led to excessive emissions of carbon dioxide, leading to global warming, and measures to reduce atmospheric carbon dioxide concentrations are needed to overcome this global challenge. Therefore, exploring an environmentally friendly strategy for capturing airborne CO 2 and converting it into high‐value‐added chemicals offers a promising pathway toward “carbon neutrality”. In recent years, porous organic polymers have attracted much attention for carbon capture and the catalytic conversion of carbon dioxide because of their high specific surface area, high chemical stability, nanoscale porosity, and structural versatility, which make them easy to functionalize. In this review, we introduce the preparation methods for various POPs, the types of POPs adsorbed during carbon dioxide capture, and the progress in the use of POPs for the photocatalytic and chemicatalytic conversion of carbon dioxide, with a special discussion on the influence of adsorption type on the efficiency of catalytic conversion. Finally, we propose a…

Abstract The escalating concern regarding the release of CO 2 into the atmosphere poses a significant threat to the contemporary efforts in mitigating climate change. Amidst a multitude of strategies for curtailing CO 2 emissions, the electrochemical CO 2 reduction presents a promising avenue for transforming CO 2 molecules into a diverse array of valuable gaseous and liquid products, such as CO, CH 3 OH, CH 4 , HCO 2 H, C 2 H 4 , C 2 H 5 OH, CH 3 CO 2 H, 1‐C 3 H 7 OH and others. The mechanistic investigations of gaseous products (e. g. CO, CH 4 , C 2 H 4 , C 2 H 6 and others) broadly covered in the literature. There is a noticeable gap in the literature when it comes to a comprehensive summary exclusively dedicated to coherent roadmap for the designing principles for a selective catalyst all possible liquid products (such as CH 3 OH, C 2 H 5 OH, 1‐C 3 H 7 OH, 2‐C 3 H 7 OH, 1‐C 4 H 9 OH, as well as other C 3 ‐C 4 products like methylglyoxal and 2,3‐furandiol, in addition to HCO 2 H, AcOH, oxalic acid and others), selectively converted by CO 2 reduction. This entails a meticulous…

Mechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent-free alternative to traditional solution-based chemistry. Mechanochemistry not only provides the opportunity to eliminate bulk solvent use, reducing waste generation, but also unveils a new reaction strategy which enables the realization of reactions previously inaccessible in solution. While the majority of organic reactions facilitated by mechanical force traditionally follow two-electron transfer pathways similar to their solution-based counterparts, the field of mechanochemically induced single-electron transfer (SET) reactions has witnessed rapid development. This review outlines examples of mechanochemical reactions facilitated by the SET process, focusing on the reagents that initiate SET, thereby positioning mechanochemistry as a burgeoning field within the realm of single-electron chemistry.

Today, rechargeable batteries are omnipresent and essential for our existence. In order to improve the electrochemical performance of electric fields, the introduction of electrolytes with fluorine (F)-based inorganic elemental compositions is a direction of exploration. However, most fluorocarbons have a high global warming potential and ozone depletion potential, which do not meet the sustainability requirements of the battery industry. Therefore, developing sustainable electrolytes is a viable option for future battery development. Although researchers have made much progress in electrolyte optimization, little attention has been paid to developing low-toxic and safe electrolytes. This review aims to elucidate the design principles and recent advances in this direction for solvents and salts. It concludes with a summary and outlook on future research directions for the molecular design of green electrolytes for practical high-voltage rechargeable batteries.

It is greatly crucial to develop low-cost energy storage candidates with high safety and stability to replace alkali metal systems for a sustainable future. Recently, aqueous zinc-ion batteries (ZIBs) have received tremendous interest owing to their low cost, high safety, wide oxidation states, and sophisticated fabrication process. Nanostructured manganese (Mn)-based oxides in different polymorphs are the potential cathode materials for the widespread application of ZIBs. However, Mn-based oxide materials suffer from several drawbacks, such as low electronic/ionic conductivity and poor cycling performance. To overcome these issues, various structural modification strategies have been adopted to enhance their electrochemical activity, including phase/defect engineering, doping with foreign atoms (e. g., metal and/or nonmetal atoms), and coupling with carbon materials or conducting polymers. Herein, this review targets to summarize the advantages and disadvantages of the above-mentioned strategies to improve the electrochemical performance of the cathodic part of ZIBs. The challenges…

Photosynthesis, converting sustainable solar energy into chemical energy, has emerged as a promising craft to achieve diverse organic transformations due to its mild reaction conditions, sustainability, and high efficiency. The synthesis of sulfonated compounds has drawn significant attention in the pharmaceuticals, agrochemicals, and materials industries due to the unique structure and electronic properties of the sulfonyl groups. Over the past decades, many photocatalytic sulfonylation reactions have been developed. In this review, the recent advances in photocatalyzed sulfonylation have been reviewed since 2020, with a primary focus on discussing reaction design and mechanism.

The pyridine core is a crucial component in numerous FDA-approved drugs and Environmental Protection Agency (EPA) regulated agrochemicals. It also plays a significant role in ligands for transition metals, alkaloids, catalysts, and various organic materials with diverse properties, making it one of the most important structural frameworks. However, despite its significance, direct and selective functionalization of pyridine is still relatively underdeveloped due to its electron-deficient nature and the strong coordinating ability of nitrogen. Among the variety of synthetic transformation, direct functionalization of C-H bond is straightforward and atom economical approach and it's advantageous for late-stage functionalization of pyridine containing drugs. In recent years, innovative strategies for regioselective C-H functionalization of pyridines and azines have emerged, offering numerous benefits such as high regioselectivity, mild conditions, and enabling transformations that were challenging with traditional methods. This review emphasizes the latest advancements in meta and…

Abstract Hyperpolarized 129Xe gas was FDA‐approved as an inhalable contrast agent for magnetic resonance imaging of a wide range of pulmonary diseases in December 2022. Despite the remarkable success in clinical research settings, the widespread clinical translation of HP 129Xe gas faces two critical challenges: the high cost of the relatively low‐throughput hyperpolarization equipment and the lack of 129Xe imaging capability on clinical MRI scanners, which have narrow‐bandwidth electronics designed only for proton (1H) imaging. To solve this translational grand challenge of gaseous hyperpolarized MRI contrast agents, here we demonstrate the utility of batch‐mode production of proton‐hyperpolarized diethyl ether gas via heterogeneous pairwise addition of parahydrogen to ethyl vinyl ether. An approximately 0.1‐liter bolus of hyperpolarized diethyl ether gas was produced in 1 second and injected in excised rabbit lungs. Lung ventilation imaging was performed using sub‐second 2D MRI with up to 2×2 mm2 in‐plane resolution using a clinical 0.35 T MRI scanner without any modifications.…

This review provides a comprehensive overview of mono-alkylation methodologies targeting crucial nitrogen moieties - amines, amides, and sulfonamides - found in organic building blocks and pharmaceuticals. Emphasizing the intersection of chemical precision with drug discovery, the central challenge addressed is achieving one-pot mono-selective short-chain N-alkylations (methylations, ethylations, and n-propylations), preventing undesired overalkylation. Additionally, sustainable, safe, and benign alternatives to traditional alkylating agents, including alcohols, carbon dioxide, carboxylic acids, nitriles, alkyl phosphates, quaternary ammonium salts, and alkyl carbonates, are explored. This review, categorized by the nature of the alkylating agent, aids researchers in selecting suitable methods for mono-selective N-alkylation.

Transitioning towards a circular economy, extensive research has focused on dynamic covalent bonds (DCBs) to pave the way for more sustainable materials. These bonds enable debonding and rebonding on demand, as well as facilitating end-of-life recycling. Acylhydrazone/hydrazone chemistry offers a material with high stability under neutral and basic conditions making it a promising candidate for materials research, though the material is susceptible to acid degradation. However, this degradation under acidic conditions can be exploited, making it widely applicable in self-healing and biomedical fields, with potential for reprocessing and recycling. This review highlights studies exploring the reversibility of acylhydrazone/hydrazone bonds in various polymers, altering their properties, and utilizing them in applications such as self-healing, reprocessing, and recycling. The review also focuses on how the mechanical properties are affected by the presence of dynamic linkages, and methods to improve the mechanical performance.

Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon-carbon and carbon-heteroatom bonds. The synthetic applications of photoinduced aryl radical formation in the synthesis of complex organic compounds, including natural products, physiologically significant molecules, and functional materials, have received immense attention. An overview of current developments in photoinduced aryl radical production methods and their uses in organic synthesis is given in this article. A generalized idea of how to choose the reagents and approach for the generation of aryl radicals is described, along with photoinduced techniques and associated mechanistic insights. Overall, this article offers a critical assessment of the mechanistic results as well as the selection of reaction parameters for specific reagents in the context of radical cascades, cross-coupling reactions, aryl radical functionalization, and selective C-H functionalization of aryl substrates.

Platinum complexes are potential antitumor drugs in chemotherapy. Their impact on tumor treatment could be greatly strengthened by combining with immunotherapy. Increasing evidences indicate that the antitumor activity of platinum complexes is not limited to chemical killing effects, but also extends to immunomodulatory actions. This review introduced the general concept of chemoimmunotherapy and summarized the progress of platinum complexes as chemoimmunotherapeutic agents in recent years. Platinum complexes could be developed into inducers of immunogenic cell death, blockers of immune checkpoint, regulators of immune signaling pathway, and modulators of tumor immune microenvironment, etc. The synergy between chemotherapeutic and immunomodulatory effects reinforces the antitumor activity of platinum complexes, and helps them circumvent the drug resistance and systemic toxicity. The exploration of platinum complexes for chemoimmunotherapy may create new opportunities to revive the discovery of metal anticancer drugs.

Abstract Enzymes turnover substrates into products with amazing efficiency and selectivity and as such have great potential for use in biotechnology and pharmaceutical applications. However, details of their catalytic cycles and the origins surrounding the regio‐ and chemoselectivity of enzymatic reaction processes remain unknown, which makes the engineering of enzymes and their use in biotechnology challenging. Computational modelling can assist experimental work in the field and establish the factors that influence the reaction rates and the product distributions. A popular approach in modelling is the use of quantum mechanical cluster models of enzymes that take the first‐ and second coordination sphere of the enzyme active site into consideration. These QM cluster models are widely applied but often the results obtained are dependent on model choice and model selection. Herein, we show that QM cluster models can give highly accurate results that reproduce experimental product distributions and free energies of activation within several kcal mol−1, regarded that large cluster…

The discovery and synthetic applications of novel organoselenium compounds and their reactions proceeded rapidly during the past fifty years and such processes are now carried out routinely in many laboratories. At the same time, the growing demand for new enantioselective processes provided new challenges. The convergence of selenium chemistry and asymmetric synthesis led to key developments in the 1970s, although the majority of early work was based on stoichiometric processes. More recently, greater emphasis has been placed on greener catalytic variations, along with the discovery of novel reactions and a deeper understanding of their mechanisms. The present review covers the literature in this field from 2010 to early 2023 and encompasses asymmetric reactions mediated by chiral selenium-based reagents, auxiliaries, and especially, catalysts. Protocols based on achiral selenium compounds in conjunction with other species of chiral catalysts, as well as reactions that are controlled by chiral substrates, are also included.

Abstract Herein, we synthesized two donor‐acceptor (D‐A) type small organic molecules with self‐assembly properties, namely MPA‐BT‐BA and MPA‐2FBT‐BA, both containing a low acidity anchoring group, benzoic acid. After systematically investigation, it is found that, with the fluorination, the MPA‐2FBT‐BA demonstrates a lower highest occupied molecular orbital (HOMO) energy level, higher hole mobility, higher hydrophobicity and stronger interaction with the perovskite layer than that of MPA‐BT‐BA. As a result, the device based‐on MPA‐2FBT‐BA displays a better crystallization and morphology of perovskite layer with larger grain size and less non‐radiative recombination. Consequently, the device using MPA‐2FBT‐BA as hole transport material achieved the power conversion efficiency (PCE) of 20.32 % and remarkable stability. After being kept in an N2 glove box for 116 days, the unsealed PSCs’ device retained 93 % of its initial PCE. Even exposed to air with a relative humidity range of 30±5 % for 43 days, its PCE remained above 91 % of its initial condition. This study highlights the vital…

The development of novel and effective drug delivery systems aimed at enhancing therapeutic profile and efficacy of therapeutic agents is a critical challenge in modern medicine. This study presents an intelligent drug delivery system based on self-assembled two-dimensional peptide nanosheets (2D PNSs). Leveraging the tunable properties of amino acid structures and sequences, we design a peptide with the sequence of Fmoc-FKKGSHC, which self-assembles into 2D PNSs with uniform structure, high biocompatibility, and excellent degradability. Covalent attachment of thiol-modified doxorubicin (DOX) drugs to 2D PNSs via disulfide bond results in the peptide-drug conjugates (PDCs), which is denoted as PNS-SS-DOX. Subsequently, the PDCs are encapsulated within the injectable, thermosensitive chitosan (CS) hydrogels for drug delivery. The designed drug delivery system demonstrates outstanding pH-responsiveness and sustained drug release capabilities, which are facilitated by the characteristics of the CS hydrogels. Meanwhile, the covalently linked disulfide bond within the PNS-SS-DOX is…

Sodium-ion batteries have abundant sources of raw materials, uniform geographical distribution, and low cost, and it is considered an important substitute for lithium-ion batteries. Thereinto, solid-state sodium-ion batteries have the advantages of low raw material cost, high safety, and high energy density, and it has shown great potential for application in the fields of mobile power, electric vehicles, and large-scale energy storage systems. However, the commercial development and large-scale application of solid-state sodium-ion batteries urgently need to address issues such as the low room-temperature ionic conductivity of solid electrolytes, high interfacial charge transfer impedance, and poor compatibility and contact between the solid electrolytes and the electrodes. Herein, this paper systematically discusses the basic theories of solid-state sodium-ion batteries, including working principles and characteristics, electrode materials and components, and solid electrolytes. Then, focusing on solid electrolytes, the key scientific challenges faced by solid-state sodium-ion…

In pursuit of high energy density, lithium metal batteries (LMBs) are undoubtedly the best choice. However, leakage and inevitable dendrite growth in liquid electrolytes seriously hinder its practical application. Solid/quasi-solid state electrolytes have emerged as an answer to solve the above issues. Especially, polymer electrolytes with excellent interface compatibility, high flexibility, and ease of machining have become a research hotspot for LMBs. Nevertheless, the interface contact between polymer electrolyte and inorganic electrode materials and the low ionic conductivity restrict its development. On account of these, in situ polymerized polymer electrolyte is proposed. Polymer solid electrolytes produced through in situ polymerization promote robust interface contact between the electrolyte and electrode while simplifying the preparation steps. This review summarized the latest research progress in in situ polymerized solid electrolytes for LMBs. These electrolytes were divided into three parts according to their polymerization methods: thermally induced polymerization,…

The past few decades have witnessed tremendous development within epoxides. Among the many known reactions involving epoxide, Meinwald rearrangements represent one of the most important and attractive approaches, which can transform epoxides into versatile carbonyl compounds. Given the high efficiency of this protocol, substantial efforts have been made by researchers by utilizing multiple catalyst systems. This review provides an overview of recent advances in the Meinwald rearrangement (from 2014 onward), along with detailed discussions on mechanistic insights. This review aims to highlight the importance and value of these methodologies, thereby promoting further investigation and application.

Hypervalent iodine reagents are versatile and readily accessible reagents that have been extensively applied in contemporary synthesis in modern organic chemistry. Among them, iodonitrene (ArI=NR), is a powerful reactive species, widely used for a single-nitrogen-atom insertion reaction, and skeletal editing to construct N-heterocycles. Skeletal editing with reactive iodonitrene components has recently emerged as an exciting approach in modern chemical transformation. These reagents have been extensively used to produce biologically relevant heterocycles and functionalized molecular architectures. Recently, the insertion of a nitrogen-atom into hydrocarbons to generate N-heterocyclic compounds using hypervalent iodine reagents has been a significant focus in the field of molecular editing reactions. In this review, we discuss the rapidly emerging field of nitrene insertion, including skeletal editing and nitrogen insertion, using hypervalent iodine reagents to access nitrogen-containing heterocycles, and the current mechanistic understanding of these processes.

Carbon dots (CDs) are novel carbon-based luminescent materials with wide-ranging applications in biosensing, bioimaging, drug transportation, optical devices, and beyond. Their advantageous attributes, including biocompatibility, biodegradability, antioxidant activity, photostability, small particle size (<10 nm), and strong light absorption and excitation across a broad range of wavelengths, making them promising candidates in the field of photodynamic therapy (PDT) as photosensitizers (PSs). Further enhancements in functionality are imperative to enhance the effectiveness of CDs in PDT applications, notwithstanding their inherent benefits. Recently, doping agents and solvents have been demonstrated to improve CDs' optical properties, solubility, cytotoxicity, and organelle targeting efficiency. These improvements result from modifications to the CDs' carbon skeleton matrices, functional groups on the surface state, and chemical structures. This review discusses the modification of CDs with heteroatom dopants, dye dopants, and solvents to improve their physicochemical and optical…

Abstract Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f15d16s2 in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X‐ray absorption spectroscopy (XAS) or X‐ray absorption near‐edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L3 edge have the advantage of a high penetration depth, enabling in‐situ reaction studies in a time‐resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L3 XANES? This article provides an overview of the information that can be extracted from experimental Ce L3 XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented…

Abstract An iron‐catalyzed visible‐light driven decarboxylative alkoxyamination is disclosed. In the presence of FeBr 2 and TEMPO, a large array of carboxylic acids including marketed drugs and biobased molecules is turned into the corresponding alkoxyamine derivatives. The versatility of the latter offers an entry towards molecular diversity generation from abundant starting materials and catalyst. Overall, this method proposes a unified and general approach for LMCT‐based iron‐catalyzed decarboxylative functionalization.

Recent interest has surged in using heterogeneous carriers to boost synergistic photocatalysis for organic transformations. Heterogeneous catalysts not only facilitate synergistic enhancement of distinct catalytic centers compared to their homogeneous counterparts, but also allow for the easy recovery and reuse of catalysts. This mini-review summarizes recent advancements in developing heterogeneous carriers, including metal-organic frameworks, covalent-organic frameworks, porous organic polymers, and others, for synergistic catalytic reactions. The advantages of porous materials in heterogeneous catalysis originate from their ability to provide a high surface area, facilitate enhanced mass transport, offer a tunable chemical structure, ensure the stability of active species, and enable easy recovery and reuse of catalysts. Both photosensitizers and catalysts can be intricately incorporated into suitable porous carriers to create heterogeneous dual photocatalysts for organic transformations. Notably, experimental evidence from reported cases has shown that the catalytic efficacy of…

Abstract D2‐symmetric (R)‐binaphthyl‐bridged pyrenophanes containing thioether bonds were synthesized. The pyrenophanes exhibited the temperature‐induced sign inversion of circularly polarized luminescence (CPL) while maintaining the emission wavelength and reversibility. The Δglum value reached 0.02, and the FL quenching by heat was negligible. The sign inversion of CPL originates from the inversion of intramolecular excimer chirality associated with excitation dynamics. The two pyrenes form a kinetically trapped left‐handed twist excimer at low temperatures, while they form a thermodynamically favored right‐handed twist excimer at high temperatures. The thioether linkers can impart flexibility suitable for the inversion of chirality of the excimers.

Different approaches to achieve 2D supramolecular polymers, as an alternative to the covalent bottom-up approaches reported for the preparation of 2D materials, are reviewed. The significance of the operation of weak non-covalent forces to induce a lateral growth of a number of self-assembling units is collected. The examples of both thermodynamically and kinetically controlled formation of 2D supramolecular polymers showed in this review demonstrate the utility of this strategy to achieve new 2D materials with biased morphologies (nanosheets, scrolls, porous surfaces) and showing elegant applications like chiral recognition, enantioselective uptake or asymmetric organic transformations. Furthermore, elaborated techniques like seeded or living supramolecular polymerizations have been demonstrated to give rise to complex 2D nanostructures.

C-F Insertion reactions, where an organic fragment formally inserts into a carbon-fluorine bond in a substrate, are highly attractive, yet largely unexplored, methods to prepare valuable fluorinated molecules. The inherent strength of C-F bonds and the resulting need for a large thermodynamic driving force to initiate C-F cleavage often leads to sequestering of the released fluoride in an unreactive by-product. Recently, however, several groups have succeeded in overcoming this challenge, opening up the study of C-F insertion as an efficient and highly atom-economical approach to prepare fluorinated compounds. In this article, the recent breakthroughs are discussed focusing on the key conceptual advances that allowed for both C-F bond cleavage and subsequent incorporation of the released fluoride into the product.

Driven by escalating environmental concerns, synthetic chemistry faces an urgent need for a green revolution. Green chemistry, with its focus on low environmental impacting chemicals and minimized waste production, emerges as a powerful tool in addressing this challenge. Metrics such as the E-factor guide the design of environmentally friendly strategies for chemical processes by quantifying the waste generated in obtaining target products, thus enabling interventions to minimize it. Phthalocyanines (Pcs), versatile molecules with exceptional physical and chemical properties, hold immense potential for technological applications. This review aims to bridge the gap between green chemistry and phthalocyanine synthesis by collecting the main examples of environmentally sustainable syntheses documented in the literature. The calculation of the E-factor of a selection of them provides insights on how crucial it is to evaluate a synthetic process in its entirety. This approach allows for a better evaluation of the actual sustainability of the phthalocyanine synthetic process and indicates…

Abstract This work conducts a comprehensive theoretical study on the non‐covalent complexation between cyclocarbons and C 60 fullerene for the first time. The binding energy between cyclocarbons and C 60 fullerene is significantly stronger than that between two C 18 or two C 60 fullerenes, indicating a particularly strong affinity. The cyclocarbons and C 60 fullerene can spontaneously assemble into complexes in the gas phase at room temperature, and the hydrophobic effect caused by the solvent environment can promote this binding. The binding strength with C 60 fullerene increases almost linearly with the increase of cyclocarbon size, and the C 34 @C 60 dimer exhibits a perfect nano‐Saturn structure. As the ring size increases, the angle between the two cyclocarbons of the 2 : 1 trimers formed by cyclocarbons and C 60 fullerene gradually decreases. In C 60 @2 C 34 trimer, the fullerene is symmetrically surrounded by two cyclocarbons. The results on the trimers formed by cyclocarbon and C 60 fullerenes in a 1 : 2 ratio showed when the cyclocarbon sandwiched between two fullerenes is…

The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors in a controlled and selective manner. This approach facilitates the construction of aromatic carbon-carbon and carbon-heteroatom bonds. In light of the green merits and the growing importance of this technique in aryl radical chemistry, this review aims to provide an overview of the recent advance in the electrochemical generation of aryl radicals organized by the aryl radical precursor type, with a focus on the substrate scope, limitation, and underlying mechanism, thereby inspiring future work on electrochemical aryl radical generation.

π-Conjugated materials are highly attractive owing to their unique optical and electronic properties. Covalent organic frameworks (COFs) offer a great opportunity for precise arrangement of building units in a π-conjugated crystalline matrix and tuning of the properties through choice of functionalities or post-synthetic modification. With this review, we aim at summarizing both the most representative as well as emerging strategies for the synthesis of π-conjugated COFs. We give examples of direct synthesis using large, π-extended building blocks. COFs featuring fully conjugated linkages such as vinylene, pyrazine, and azole are discussed. Then, post-synthetic modification methods that result in the extension of the COF π-system are reviewed. Throughout, mechanistic insights are presented when available. In the context of their utilization as film devices, we conduct a concise survey of the prominent COF layer deposition techniques reported and their aptness for the deposition of fused aromatic systems.

The prosperity of the lithium-ion battery market is inevitably accompanied by the depletion of corresponding resources and the accumulation of spent batteries in a dialectical manner. Spent lithium-ion batteries are harboring the characteristics of hazardous waste and high-value resources, so efficient recycling is of great significance. The cathode material is considered as an interesting target for repurposing. Despite some important reviews give commendable emphasis to recycling technologies, there is still a dearth of exploration of recycling mechanisms. This deficiency of awareness highlights the need for further research and development in this area. This review aims to systematically review and thoroughly discuss the reduction reaction mechanism of each method regarding different cathode materials. And systematically digest the selection of reducing agent and the effect of reduction reaction on material regeneration are systematically digested, as well as the impact of the reduction reaction on the regeneration of materials. This review emphasizes the importance of balancing…

MXenes have unique properties such as high electrical conductivity, excellent mechanical properties, rich surface chemistry, and convenient processability. These characteristics make them ideal for producing flexible materials with tunable microstructures. This paper reviews the laboratory research progress of flexible MXene and its composite materials for supercapacitors. And introduces the general synthesis method of MXene, as well as the preparation and properties of flexible MXene. By analyzing the current research status, the electrochemical reaction mechanism of MXene was explained from the perspectives of electrolyte and surface terminating groups. This review particularly emphasizes the composite methods of freestanding flexible MXene composite materials. The review points out that the biggest problem with flexible MXene electrodes is severe self-stacking, which reduces the number of chemically active sites, weakens ion accessibility, and ultimately lowers electrochemical performance. Therefore, it is necessary to composite MXene with other electrode materials and design a…

Metal-organic cages (MOCs) are supramolecular coordination complexes that have internal cavities for hosting guest molecules and exhibiting various properties. However, the functions of MOCs are limited by the choice of the building blocks. Post-synthetic modification (PSM) is a technique that can introduce new functional groups and replace existing ones on the MOCs without changing their geometry. Among many PSM methods, covalent PSM is a promising approach to modify MOCs with tailored structures and functions. Covalent PSM can be applied to either the internal cavity or the external surface of the MOCs, depending on the functionality expected to be customized. However, there are still some challenges and limitations in the field of covalent PSM of MOCs, such as the balance between the stability of MOCs and the harshness of organic reactions involved in covalent PSMs. This concept article introduces the organic reaction types involved in covalent PSM of MOCs, their new applications after modification, and summarizes and provides an outlook of this research field.

Abstract The development of sustainable chemistry underlying the quest to minimize and/or valorize waste in the carbon‐neutral manufacture of chemicals is followed over the last four to five decades. Both chemo‐ and biocatalysis have played an indispensable role in this odyssey. in particular developments in protein engineering, metagenomics and bioinformatics over the preceding three decades have played a crucial supporting role in facilitating the widespread application of both whole cell and cell‐free biocatalysis. The pressing need, driven by climate change mitigation, for a drastic reduction in greenhouse gas (GHG) emissions, has precipitated an energy transition based on decarbonization of energy and defossilization of organic chemicals production. The latter involves waste biomass and/or waste CO 2 as the feedstock and green electricity generated using solar, wind, hydroelectric or nuclear energy. The use of waste polysaccharides as feedstocks will underpin a renaissance in carbohydrate chemistry with pentoses and hexoses as base chemicals and bio‐based solvents and polymers…

Abstract Plastic pollution constitutes an evergrowing urgent environmental problem, since overaccumulation of plastic waste, arising from the immense increase of the production of disposable plastic products, overcame planet's capacity to properly handle them. Chemical upcycling of polystyrene constitutes a convenient method for the conversion of plastic waste into high‐added value chemicals, suggesting an attractive perspective in dealing with the environmental crisis. We demonstrate herein a novel, easy‐to‐perform organocatalytic photoinduced aerobic protocol, which proceeds via synergistic indirect hydrogen atom transfer (HAT) catalysis under LED 390 nm Kessil lamps as the irradiation source. The developed method employs a BrCH2CN‐thioxanthone photocatalytic system and was successfully applied to a variety of everyday‐life plastic products, leading to the isolation of benzoic acid after simple base‐acid work up in yields varying from 23–49 %, while a large‐scale experiment was successfully performed, suggesting that the photocatalytic step is susceptible to industrial application.

Abstract The pursuit of energy‐saving materials and technologies has garnered significant attention for their pivotal role in mitigating both energy consumption and carbon emissions. In particular, thermochromic windows in buildings offer energy‐saving potential by adjusting the transmittance of solar irradiation in response to temperature changes. Radiative cooling (RC), radiating thermal heat from an object surface to the cold outer space, also offers a potential way for cooling without energy consumption. Accordingly, smart window and RC technologies based on thermochromic materials can play a crucial role in improving energy efficiency and reducing energy consumption in buildings in response to the surrounding temperature. Vanadium dioxide (VO 2 ) is a promising thermochromic material for energy‐saving smart windows and RC due to its reversible metal‐to‐insulator transition, accompanying large changes in its optical properties. This review provides a brief summary of synthesis methods of VO 2 nanostructures based on nanoparticles and thin films. Moreover, this review emphasizes…

Abstract The fabrication of supramolecular light‐harvesting systems (LHS) with sequential energy transfer is of significance in utilizing light energy. In this study, we report the non‐covalent self‐assembly of a sequential LHS by pillar[5]arene‐based host‐guest interaction in water and its applications in white light‐emitting diode (LED) device and latent fingerprint imaging. The host‐guest complex WP5 G self‐assembles into nanoparticles in water and shows enhanced aggregation‐induced emission (AIE) effect. The nanoparticles can be further used to construct sequential LHS with fluorescent dyes 4,7‐di(2‐thienyl)‐benzo[2,1,3]thiadiazole (DBT) and sulforhodamine 101 (SR101). Impressively, the system shows white‐light emission when the molar ratio of WP5 G/DBT/SR101 is 1100/2/16. The material can be coated on a LED bulb to achieve white‐light emission. In addition, the sequential LHS exhibit multicolor fluorescence including red emission, which have been successfully applied to high‐resolution imaging of latent fingerprints. Therefore, we demonstrated a general strategy for the…

Abstract Ni single atom containing hollow carbon nanospheres with nitrogen doping has been synthesized by carbonization of Ni(NO 3 ) 2 /phloroglucinol‐formaldehyde polymer/silica composite. The samples have been characterized by powder X‐ray diffraction, nitrogen adsorption/desorption, electron microscopic, Raman and X‐ray photoelectron spectroscopic studies. The microstructure and surface area vary with the amount of Ni(NO 3 ) 2 employed in the syntheses and the carbonization environment. An optimized amount of nickel and argon as the carbonization gas afford Ni‐1.0@N@HCN‐Ar which possesses overall superior features. The uniformly dispersed Ni single atoms within the hollow porous carbon framework fully utilize all the electroactive sites thereby improving the supercapacitive performance. The specific capacitance of Ni‐1.0@N@HCN‐Ar reaches 777 F g −1 at 1 A g −1 with a Coulombic efficiency of 98.4 % and excellent recyclability. The energy and power density of Ni‐1.0@N@HCN‐Ar are found to be high; at 1 A g −1 its energy density is 155.4 Wh kg −1 with a power density of 600.3 W kg −1…

A viable alternative to non-renewable hydrocarbon fuels is hydrogen gas, created using a safe, environmentally friendly process like water splitting. An important role in water-splitting applications is played by the development of two-dimensional (2D) layered transition metal chalcogenides (TMDCs), transition metal carbides (MXenes), graphene-derived 2D layered nanomaterials, phosphorene, and hexagonal boron nitride. Advanced synthesis methods and characterization instruments enabled an effective application for improved electrocatalytic water splitting and sustainable hydrogen production. Enhancing active sites, modifying the phase and electronic structure, adding conductive elements like transition metals, forming heterostructures, altering the defect state, etc., can improve the catalytic activity of 2D stacked hybrid monolayer nanomaterials. The majority of global research and development is focused on finding safer substitutes for petrochemical fuels, and this review summarizes recent advancements in the field of 2D monolayer nanomaterials in water splitting for…

Surface-enhanced Raman scattering (SERS) spectroscopy, a highly sensitive technique for detecting trace-level analytes, relies on plasmonic substrates. The choice of substrate, its morphology, and the excitation wavelength are crucial in SERS applications. To address advanced SERS requirements, the design and use of efficient nanocomposite substrates have become increasingly important. Notably, magnetic-plasmonic (MP) nanocomposites, which combine magnetic and plasmonic properties within a single particle system, stand out as promising nanoarchitectures with versatile applications in nanomedicine and SERS spectroscopy. In this review, we present an overview of MP nanocomposite fabrication methods, explore surface functionalization strategies, and evaluate their use in SERS. Our focus is on how different nanocomposite designs, magnetic and plasmonic properties, and surface modifications can significantly influence their SERS-related characteristics, thereby affecting their performance in specific applications such as separation, environmental monitoring, and biological applications.…

Abstract Developing new electrode materials with good temperature‐dependent electrochemical performance has become a great issue for the deployment of hybrid supercapacitors with wide temperature tolerance. In this work, a series of Ta‐substituted SrCo 1‐x Ta x O 3‐δ (x=0.05, 0.10, 0.15, 0.20) perovskites have been studied as positive electrodes for hybrid supercapacitors in terms of their structures, elemental valence states and electrochemical performances. Incorporating Ta into SrCoO 3‐δ perovskite not only stabilizes the crystallite structure but also notably improves electrochemical activities. The SrCo 0.95 Ta 0.05 O 3‐δ @CC delivers the highest specific capacity ( Q sp ) of 227.91 C g −1 at 1 A g −1 , which is attributed to the highest oxygen vacancy content and the fastest oxygen diffusion kinetics. The hybrid supercapacitor SrCo 0.95 Ta 0.05 O 3‐δ @CC//AC@CC exhibits a high energy density of 22.82 Wh kg −1 @775.09 W kg −1 and a stable long‐term cycle life (5000 cycles) with 90.7 % capacity retention. As temperature increases from 25 to 85 °C, the capacitance properties are…

Abstract Photodynamic therapy (PDT) is a rapidly growing discipline that is expected to become an encouraging noninvasive therapeutic strategy for cancer treatment. In the PDT process, an efficient intersystem crossing (ISC) process for photosensitizers from the singlet excited state (S1) to the triplet excited state (T1) is critical for the formation of cytotoxic reactive oxygen species and improvement of PDT performance. Thermally activated delayed fluorescence (TADF) molecules featuring an extremely small singlet–triplet energy gap and an efficient ISC process represent an enormous breakthrough for the PDT process. Consequently, the development of advanced TADF photosensitizers has become increasingly crucial and pressing. The most recent developments in TADF photosensitizers aimed at enhancing PDT efficiency for bio‐applications are presented in this review. TADF photosensitizers with water dispersibility, targeting ability, activatable ability, and two‐photon excitation properties are highlighted. Furthermore, the future challenges and perspectives of TADF photosensitizers in…

Free radicals are increasingly recognized as active intermediate reactive species that can participate in various redox processes, significantly influencing the mechanistic pathways of reactions. Numerous researchers have investigated the generation of one or more distinct photogenerated radicals, proposing various hypotheses to explain the reaction mechanisms. Notably, recent research has demonstrated the emergence of photogenerated radicals in innovative processes, including organic chemical reactions and the photocatalytic dissolution of precious metals. To harness the potential of these free radicals more effectively, it is imperative to consolidate and analyze the processes and action modes of these photogenerated radicals. This conceptual paper delves into the latest advancements in understanding the mechanics of photogenerated radicals.

Abstract Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron‐oxygen‐based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen‐doped Π‐extended helical nanographene. The π‐extension induces distortion in the DOBNA‐incorporated nanographene, endowing a pair of helicenes, (P)‐B2NG, and (M)‐B2NG exhibiting circularly polarized luminescence with glum of −2.3×10−3 and +2.5×10−3, respectively. B2NG exhibited MR‐TADF with a lifetime below 5 μs, and a reasonably high fluorescence quantum yield (50 %). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens…

). The aromatic character of borazine have basically reached a consensus after a long period of controversy, but the related properties of carborazine are even rarely reported. In this work, we systematically investigated the geometric structure, charge distribution, frontier molecular orbital characteristics, bonding, electronic delocalization, magnetic shielding effect, and induced ring current of carborazine and borazine, and compared the studied characteristics with those of benzene to determine the aromatic character of the two analogues. The combination of multiple properties shows that although they are isoelectronic, carborazine is evidently aromatic, while borazine only exhibits rather weak aromaticity. The C atom acting as a connecting bridge between B and N atoms in carborazine reduces the electronegativity difference on the molecular backbone and enhances the electronic delocalization over the conjugated path, which is the essence of the distinct disparity of aromaticity between carborazine and borazine.

Abstract The ability of triaryltelluronium salts to interact with N ‐halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and in solution is demonstrated herein. Cocrystals of the triaryltelluronium bearing two CF 3 electron‐withdrawing groups per aryl ring with N ‐chloro‐, N ‐bromo‐ and N ‐iodosuccinimide (respectively NCS, NBS and NIS) were analyzed by X‐ray diffraction, evidencing a ChB between tellurium and the carbonyl group of NXS. This ChB was confirmed in solution by NMR spectroscopy, especially by 125 Te NMR titration experiment, which allowed the determination of the association constant ( K a ) between the telluronium and NBS. The so‐obtained K a value of 17.3±0.6 M −1 indicated a moderate interaction in solution because of the competitive role of the solvent. The strength of the Te⋅⋅⋅O ChB was however sufficient enough to promote the catalytic halofunctionalization of aromatics and of alkenes such as the intra‐ and intermolecular haloalkoxylation and haloesterification of alkenes.

Owing to well-defined structure as well as easy synthesis and modification, metal-organic frameworks (MOFs) have emerged as promising catalysts for tandem reactions. In this article, we aim to summarize the development of multifunctional MOFs, including mixed metal MOFs, MOFs that are synergistically catalyzed by metal nodes and organic linkers, MOFs loaded with metal nanoparticles, etc, as heterogenous catalysts for tandem reactions over the past five years. This concept briefly discusses on present challenges, future trends, and prospects of multifunctional MOFs catalysts in tandem reactions.

) and low redox potential (-3.04 V vs. standard hydrogen electrode), Lithium (Li) metal anode (LMA) received increasing attentions. However, notorious dendrite and volume expansion during the cycling process seriously hinder the development of high energy density Li metal batteries. Constructing three-dimensional (3D) current collectors for Li can fundamentally solve the intrinsic drawback of hostless for Li. Therefore, this review systematically introduces the design and synthesis engineering and the current development status of different 3D collectors in recent years (the current collectors are divided into two major parts: metal-based current collectors and carbon-based current collectors). In the end, some perspectives of the future promotion for LMA application are also presented.

Chiral macrocycles have recently emerged as promising materials for enantioselective recognition, asymmetric catalysis, and circularly polarized luminescence (CPL) due to their terminal-free structure, preorganized chiral cavities, and unique host-guest and self-assembly properties. This review summarizes recent advances in the design and synthesis of chiral macrocycles with central, axial, helical, and planar chirality, each imparting distinct structural and chiroptical characteristics. We highlight key strategies for constructing these macrocycles and their applications in optoelectronic and catalytic systems. Emphasis is placed on the balance between rigidity and flexibility in macrocycle design, essential for effective molecular recognition, adaptable catalysis, and CPL. We conclude with perspectives on future opportunities, anticipating ongoing developments in chiral macrocycle research.

Abstract A (3+3)‐cycloaddition to afford 2‐azabiyclo[3.1.1]heptanes was realized by reacting highly strained aryl bicyclo[1.1.0]butane (BCBs) carboxylates with tosylated aziridines. Under Sc(OTf)3 catalysis the transformation proceeded smoothly under mild conditions to the corresponding bicyclic products bearing at the bridgeheads of the embedded four‐membered ring aryl and ester moieties, respectively. This reaction is a rare example of a cycloaddition of two highly strained ring systems under Lewis acid catalysis. Mechanistic experiments provided insights into the reaction mechanism.

Photochemical action plots are a powerful tool for mapping photochemical reaction outcomes wavelength-by-wavelength. Typically, they map either the depletion of a reactant or the formation of a specific product as a function of wavelength. Herein, we exploit action plots to simultaneously map the formation of several photochemical products from a single chromophore. We demonstrate that the wavelength-resolved mapping of two reaction products formed during the irradiation of a chalcone species not only shows wavelength dependence - exhibiting the typical strong red-shift of the photochemical reactivity compared to the absorbance spectrum of the chromophore - but also a strong wavelength selectivity with remarkably different product distributions resulting from different irradiation wavelengths.

Buckybowls, bowl-shaped polyaromatic hydrocarbons, have received intensive interest owing to their multifaceted potentials in supramolecular chemistry and materials science. Buckybowls possess unique chemical and physical properties associated with their concave and convex faces. In view of the shape complementarity, which is one of the key factors for host-guest assembly, buckybowls are ideal receptors for fullerenes. In fact, the host-guest assembly between buckybowls and fullerenes is one of the most active topics in buckybowls chemistry, and the resulting supramolecular materials show promising applications in optoelectronics, biomaterials, and so forth. In this tutorial review, we present an overview for the progress on fullerene receptors based on buckybowls over the last decade.

Although it is well-known that the Lewis acidity of Metal-Organic Frameworks (MOFs) can effectively enhance their catalytic activity in organic transformations, access to these Lewis-acidic sites remains a key hurdle to widespread applications of Lewis-acidic catalysis by MOFs. Easy accessibility of strong Lewis acidic sites onto 2D MOFs by using proper activation methods can be a cornerstone in attaining desired catalytic performance. Herein, we report a new 2D chemically stable MOF, IITKGP-60, which displayed excellent framework robustness over a wide pH range (2-12). Benefiting from the abundant open metal sites (OMSs) and framework robustness, the catalytic activity of the developed material was explored in one-pot three-component Strecker reaction and Knoevenagel condensation reaction. Moreover, the developed catalyst is superior in catalyzing the reactions involving sterically hindered substrate (1-naphthaldehyde) with high turnover number. A comparative catalytic study was conducted using different activation methods (chloroform and methanol exchanged activated samples),…

Abstract Inorganic‐organic hybrid materials are a kind of multiduty materials with high crystallinity and definite structures, built from functional inorganic and organic components with highly tunable photochemical properties. Perylenediimides (PDIs) are a kind of strong visible light‐absorbing organic dyes with π‐electron‐deficient planes and photochemical properties depending on their micro‐environment, which provides a platform for designing tunable and efficient hybrid photocatalytic materials. Herein, four radical‐doped PDI‐based crystalline hybrid materials, Cl4‐PDI⋅SiW12O40 (1), Cl4‐PDI⋅SiMo12O40 (2), Cl4‐PDI⋅PW12O40 (3), and Cl4‐PDI⋅PMo12O40 (4), were attained by slow diffusion of polyoxometalates (POMs) into acidified Cl4‐PDI solutions. The obtained PDI‐based crystalline hybrid materials not only exhibited prominent photochromism, but also possessed reactive organic radicals under ambient conditions. Furthermore, all hybrid materials could be easily photoreduced to their radical anions (Cl4‐PDI⋅−), and then underwent a second photoexcitation to form energetic excited state…

Abstract Aluminum‐ion batteries (AIBs) are promising electrochemical energy storage sources because of their high theoretical specific capacity, light weight, zero pollution, safety, inexpensiveness, and abundant resources. These theoretical advantages have recently made AIBs a research hotspot. However, electrolyte‐related issues significantly limit their commercialization. The electrolyte choices for AIBs are significantly limited, and most of the available options do not facilitate the Al3+/Al three‐electron transfer reaction. Thus, this review presents an overview of recent advances in electrolytes and modification strategies for AIBs to clarify the limitations of existing AIB electrolytes and offer guidance for improving their performance. Furthermore, herein, the advantages, limitations and possible solutions for each electrolyte are discussed, after which the future of AIB electrolytes is envisioned.

Herein we describe a sustainable and efficient photocatalytic method for the stereoselective radical alkylation of chiral sulfinyl imines. By employing readily available non-prefunctionalized radical precursors and the cost-effective TBADT as a direct HAT photocatalyst, we successfully obtain diverse chiral amines with high yields and excellent diastereoselectivity under mild conditions. This method provides an efficient approach for accessing a diverse array of medicinally relevant compounds, including both natural and synthetic α-amino acids, aryl ethyl amines, and other structural motifs commonly found in approved pharmaceuticals and natural product.

Transition-metal catalyzed tandem asymmetric reactions were powerful tools to access various chiral compounds. Many strategies have been developed for the coupling of 1,n-dienes with aryl halides via a tandem Heck/Tsuji-Trost process. However, the control of regio- and stereo-chemistry remains a challenging task. This minireview details the recent advances in the field of asymmetric Heck/Tsuji-Trost reactions catalyzed by palladium complex, which have opened new opportunities and expanded our understanding in this area of research in recent years.

Aqueous Zn-metal batteries (AZMBs) hold a promise as the next-generation energy storage devices due to their low cost and high specific energy. However, the actual energy density falls far below the requirements of commercial AZMBs due to the use of excessive Zn as anode and the associated issues including dendritic growth and side reactions. Reducing the N/P ratio (negative capacity/positive capacity) is an effective approach to achieve high energy density. A significant amount of research has been devoted to increasing the cathode loading and specific capacity or tuning the Zn anode utilization to achieve low N/P ratio batteries. Nevertheless, there is currently a lack of comprehensive overview regarding how to enhance the utilization of the Zn anode to balance the cycle life and energy density of AZMBs. In this review, we summarize the challenges faced in achieving high-utilization Zn anodes and elaborate on the modifying strategies for the Zn anode to lower the N/P ratio. The current research status and future prospects for the practical application of high-performance AZMBs are…

Abstract Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long‐term solution for large‐scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg2+:−2.37 V vs. SHE) and high natural abundance. To develop viable magnesium batteries with high energy density, the electrolytes must meet a range of requirements: high ionic conductivity, wide electrochemical potential window, chemical compatibility with electrode materials and other battery components, favourable electrode‐electrolyte interfacial properties and cost‐effective synthesis. In recent years, significant progress in electrolyte development has been made. Herein, a comprehensive overview of these advancements is presented. Beginning with the early developments, we particularly focus on the chemical aspects of the electrolytes and their correlations with electrochemical properties. We also highlight the design of new anions for practical electrolytes, the use of electrolyte additives to optimize anode‐electrolyte…

Acenes, the group of polycyclic aromatic hydrocarbons (PAHs) with linearly fused benzene rings, possess distinctive electronic properties with potential applicability in material science. Hexacene was the largest acene obtained and characterized in the last century, followed by heptacene in 2006. Since then, a race for obtaining the largest acene resulted in the development of several members of this family as well as diverse innovative synthetic strategies, from solid-state chemistry to the promising on-surface chemistry. This last technique allows the obtention of large acenes, up to tridecacene, the largest acene so far. This review presents the different methodologies employed for the synthesis of acenes, highlighting the newest studies, to provide a much more thorough understanding of the essence of the electronic structure of this captivating group of organic compounds.

Diketopyrrolopyrrole (DPP)-based polymer semiconductors have drawn great attention in the field of organic electronics due to the planar structure, decent solubilizing capability, and high crystallinity. However, the electron-deficient capacity of DPP derivatives are not strong enough, leading to relatively high-lying lowest unoccupied molecular orbital (LUMO) energy levels of the corresponding polymers. As a result, n-type and ambipolar DPP-based polymers are rare and their electron mobilities also lag far behind the p-type counterparts, which limits the development of important p-n-junction-based electronic devices. Therefore, new design strategies have been proposed recent years to develop n-type/ambipolar DPP-based polymers with improved performances. In this view, these molecular design strategies are summarized, including copolymerization of DPP with different acceptors and weak donors, DPP flanked aromatic ring modification, DPP-core ring expansion and DPP dimerization. The relationship between the chemical structures and organic thin-film transistor performances is…

Carbon dots (C-dots) obtained from D-glucose have attracted great interest because of their properties and as a model for understanding the synthesis process and the origin of photoluminescence in carbon-based nanostructures. Synthesising C-dots under hydrothermal conditions has become one of the most common methods for their preparation. Understanding the details of this process is quite difficult. To tackle this challenge, we have adopted a multi-technique approach in our present work. We have correlated different spectroscopic analyses, such as infrared, Raman, fluorescence, NMR, and UV-Vis, to connect the emissions with specific chemical groups. In particular, in situ infrared analysis as a function of temperature has allowed following the formation of C=C, C=O, and COOH species and the rise of specific emissions. Only weak emissions due to n-π* transitions are detected upon post-synthesis thermal annealing.

Abstract Organoalkali compounds have undergone a far‐reaching transformation being a coupling partner to a mediator in unusual organic conversions which finds its spot in the field of sustainable synthesis. Transition‐metal catalysis has always been the priority in C(sp3)−H bond functionalization, however alternatively, in recent times this has been seriously challenged by earth‐abundant alkali metals and their complexes arriving at new sustainable organometallic reagents. In this line, the importance of MN(SiMe3)2 (M=Li, Na, K & Cs) reagent revived in C(sp3)−H bond functionalization over recent years in organic synthesis is showcased in this minireview. MN(SiMe3)2 reagent with higher reactivity, enhanced stability, and bespoke cation‐π interaction have shown eye‐opening mediated processes such as C(sp3)−C(sp3) cross‐coupling, radical‐radical cross‐coupling, aminobenzylation, annulation, aroylation, and other transformations to utilize readily available petrochemical feedstocks. This article also emphasizes the unusual reactivity of MN(SiMe3)2 reagent in unreactive and robust C−X…

Abstract Lipophilic biphenylthiophene‐ and phenanthrothiophene‐triazine compounds, BPTT n and CPTT n , respectively, were prepared by a tandem procedure involving successive Suzuki‐Miyaura coupling and Scholl cyclodehydrogenation reactions. These compounds display photoluminescence in solution and in thin film state, solvatochromism with increasing solvent's polarity, as well as acidochromism and metal ion recognition stimuli‐responsive fluorescence. Protonation of BPTT 10 and CPTT 10 by trifluoroacetic acid results in fluorescence quenching, which is reversibly restored once treated with triethylamine (ON‐OFF switch). DFT computational studies show that intramolecular charge transfer (ICT) phenomena occurs for both molecules, and reveal that protonation enhances the electron‐withdrawing ability of the triazine core and reduces the band gap. This acidochromic behavior was applied to a prototype fluorescent anti‐counterfeiting device. They also specifically recognize Fe 3+ through coordination, and the recognition mechanism is closely related to the photoinduced electron transfer…

Abstract Processing CO2 into value–added chemicals and fuels stands as one of the most crucial tasks in addressing the global challenge of the greenhouse effect. In this study, we focused on the complex (dpp–bian)NiBr2 (where dpp–bian is di‐isopropylphenyl bis‐iminoacenaphthene) as a precatalyst for the electrochemical reduction of CO2 into CH4 as the sole product. Cyclic voltammetry results indicate that the realization of a catalytically effective pattern requires the three–electron reduction of (dpp–bian)NiBr2. The chemically reduced complexes [K(THF)6]+[(dpp–bian)Ni(COD)]− and [K(THF)6]+[(dpp–bian)2Ni]− were synthesized and structurally characterized. Analyzing the data from the electron paramagnetic resonance study of the complexes in solutions, along with quantum–chemical calculations, reveals that the spin density is predominantly localized at their metal centers. The superposition of trajectory maps of the electron density gradient vector field and the electrostatic force density field per electron, as well as the atomic charges, discloses that, within the first coordination…

Abstract Quantum chemical calculations of the anions AeF − (Ae=Be−Ba) have been carried out using ab initio methods at the CCSD(T)/def2‐TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge‐ and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F − donate electronic charge into the vacant sp x (σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae F − . The heavier Ae atoms Ca, Sr, Ba use their vacant (n‐1)d AOs as acceptor orbitals which enables them to form a second σ donor bond with F − that leads to quadruply bonded Ae F − (Ae=Ca−Ba). The presentation of molecular orbitals or charge distribution using only one isodensity value may give misleading information about the overall nature of the orbital or charge distribution. Better insights are given by contour line diagrams. The…

Abstract High‐resolution nuclear magnetic resonance (NMR) spectroscopy represents a key methodology for studying biomolecules and their interplay with other molecules. Recent developments in labeling strategies have made it possible to incorporate fluorine into proteins and peptides reliably, with manageable efforts and, importantly, in a highly site‐specific manner. Paired with its excellent NMR spectroscopic properties and absence in most biological systems, fluorine has enabled scientists to investigate a rather wide range of scientific objectives, including protein folding, protein dynamics and drug discovery. Furthermore, NMR spectroscopic experiments can be conducted in complex environments, such as cell lysate or directly inside living cells. This review presents selected studies demonstrating how 19F NMR spectroscopic approaches enable to contribute to the understanding of biomolecular processes. Thereby the focus has been set to labeling strategies available and specific NMR experiments performed to answer the underlying scientific objective.

Abstract Although metal‐organic frameworks (MOFs) and metalo hydrogen‐bonded organic frameworks (MHOFs) are designed as promising solid‐state proton conductors by incorporating various protonic species intrinsically or extrinsically, design and development of such materials by employing the concept of proton conduction through coordinated polar protic solvent is largely unexplored. Herein, we have constructed two proton‐conducting materials having different solvent coordinated metal cationic species: In‐H 2 O‐MOF , ({[In(H 2 O) 6 ][In 3 (Pzdc) 6 ] ⋅ 15H 2 O} n ; H 2 Pzdc: pyrazine‐2,3‐dicarboxylic acid) with coordinated water molecules from hexaaquaindium cationic species, and MHOF‐4 , ([{Co(NH 3 ) 6 } 2 (2,6‐NDS) 2 (H 2 O) 2 ] n ; 2,6‐H 2 NDS: 2,6‐naphthalenedisulfonic acid) with coordinated ammonia from hexaammoniacobalt cationic species. Interestingly, higher proton conductivity was achieved for In‐H 2 O‐MOF (1.5×10 −5 S cm −1 ) than MHOF‐4 (6.3×10 −6 S cm −1 ) under the extreme conditions (80 °C and 95 % RH), which could be attributed to enhanced acidity of coordinated water…

Chiral Metal-Organic Frameworks (CMOFs) is a kind of material with great application value in recent years. Formed by the coordination of metal ions or metal clusters with organic ligands. It has ordered and adjustable pores, multi-dimensional network structure, large specific surface area and excellent adsorption properties. This material structure combines the properties of metal-organic frameworks (MOFs) with the chiral properties of chiral molecules. It has great advantages in catalysis, adsorption, separation and other fields. Therefore, it has a wide range of applications in chemistry, biology, medicine and materials science. In this paper, various synthesis strategies and preparation methods of chiral metal-organic frameworks are reviewed from different perspectives, and the advantages of each method are analyzed. In addition, the applications of chiral metal-organic framework materials in enantiomer recognition and separation, circular polarization luminescence and asymmetric catalysis are systematically summarized, and the corresponding mechanisms are discussed. Finally,…

Abstract Utilizing photocatalytic method to produce hydrogen by splitting water is an efficient strategy to solve the hotspot issues of energy crisis and environmental pollution. Herein, we systematically investigate the corresponding properties of the reported Cu‐bearing ternary compound monolayer CuP 2 Se by using the first‐principle calculations. The monolayer CuP 2 Se has quite small cleavage energy of 0.51 J/m 2 , indicating it can be easily produced by the mechanical exfoliation method experimentally. In addition, it is an indirect bandgap semiconductor material which has a moderate value of 1.91 eV. The conduction band minimum (CBM) and valence band maximum (VBM) can perfectly straddle the redox potentials of water when a biaxial strain of −4% to 4% is applied, unveiling the high photocatalytic thermodynamic stability of monolayer CuP 2 Se in response to the effect of solvent tension. Remarkably, the monolayer CuP 2 Se also demonstrates significant sunlight capturing ability in the visible region. The outstanding electronic and optical properties suggest that the monolayer…

Abstract In this review, the impact of the transition from today's resource‐wasting petrochemical economy towards a 100/100 renewable and biodegradable future is discussed with respect to the fragrance families: “citrus”, “green”, “fruity”, “floral”, “floriental”, “oriental”, “woody”, “chypre” and “fougère”. After benchmark data on ingredients usage, definitions on biodegradation and sustainability are given. Celebrating the 150th anniversary of synthetic vanillin, its historic synthesis from renewable starting materials serves as introduction. In the grand scheme of things, citrus scents upcycled from the beverages industry, are already an ideal case for 100/100 with new opportunities for artificial essential oils. In the fruity domain, transparent and lactonic ingredients are available in a sustainable manner. However, in the domain of green odorants, there is a lack of green chemistry for important key materials. In the floral family, renewability is more critical than biodegradability, but cost is an issue. Thanks to Ambrox and maltol, florientals and orientals will persist,…

Light-mediated processes have received significant attention, since they have re-surfaced unconventional reactivity platforms, complementary to conventional polar chemistry. γ-Lactones and cyclopropanes are prevalent moieties, found in numerous natural products and pharmaceuticals. Among various methods for their synthesis, light-mediated protocols are coming to the spotlight, although these are contingent upon the use of photoorgano- or metal-based catalysts. Herein, we introduce a novel photochemical activation of iodo-reagents via the use of cheap sodium ascorbate or ascorbic acid to enable their homolytic scission and addition onto double bonds. The developed protocol was applied successfully to the formal [3+2] cycloaddition for the synthesis of γ-lactones, traditional atom transfer radical addition (ATRA) reactions and the one-pot two-step conversion of alkenes to cyclopropanes. In all cases, the desired products were obtained in good to high yields, while the reaction mechanism was thoroughly investigated. Depending on the nature of the iodo-reagent, a halogen or a…

Although the 3 d transition-metal catalyzed C-H functionalization have been extensively employed to promote the formation of valuable carbon-carbon bonds, the persistent problems, including the use of sensitive Grignard reagents and the rigorous operations (solvent-drying, inert gas protection, metal pre-activation and RMgX addition rate control), still leave great room for further development of sustainable methodologies. Herein, we report a mechanochemical technology toward in-situ preparation of highly sensitive organomagnesium reagents, and thus building two general 3 d transition-metal catalytic platforms that enables regioselective arylation and alkylation of indoles with a wide variety of halides (including those containing post transformable functionalities and heteroaromatic rings). This mechanochemical strategy also brings unique reactivity and high step-economy in producing functionalized N-free indole products.

This work establishes the first direct mechanocatalytic reaction protocol within an extruder, focusing on the Suzuki-Miyaura reaction. Through the coating of either the extruder screws or barrel with Pd, we executed the cross-coupling reaction without the reliance on molecular catalyst compounds or powders, and solvents continuously. We identified the influence and interplay of crucial reaction parameters such as temperature, mechanical energy input, residence time, rheology, and catalyst contact time and finally obtained 36 % and 75 % of the reaction product after one and four reactor passes respectively.

Abstract Nano‐sized high‐entropy materials (HEMs) recently received more attention to researchers due to their superior electrochemical catalytic properties. HEMs comprise at least five elements with or without metals and are synthesized through solid‐state reactions and solution‐mediated techniques. The presence of many elements in these HEMs result in a high mixing entropy and facilitates the formation of stable solid solutions in fundamental crystal structures. Herein, Pt‐free high‐entropy alloys (HEAs) were synthesized through facile and straightforward pulse microwave (PM) synthesis technique, which serve as efficient electrochemical catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The PM synthesis method was conducted at an extremely low temperature (100 °C) without any external catalytic reagents. Using this PM technique, Cr18.2Zr13.5Ti5.3Co17.8Ni8.4Cu8.5Fe28.3 and Al15.3Mn18.2Ti3.7Co23.2Ni5.9Cu5.9Fe27.8 HEAs catalysts were synthesized with superior catalytic activity towards OER and ORR and compare its activities with pure Pt catalysts.…

Abstract Monitoring mercury (Hg) is critical for environmental and public health. Metal‐organic framework (MOF)‐based sensors demonstrate the advantage of high sensitivity and rapid response. We summarize the advances of MOF sensors for Hg2+ detection from the perspective of MOF type and role in the sensors. First, we introduce three MOFs used in Hg sensors‐UIO, ZIF, and MIL‐that have demonstrated superior performance. Then, we discuss the specifics of MOF‐based sensors for Hg2+ detection in terms of the recognition and signal elements. Currently, the recognition elements include T‐rich aptamers, noble metal nanoparticles, central metal ions, and organic functional groups inherent to MOFs. Sensors with fluorescence and colorimetric signals are the two main types of optical MOF sensors used for Hg detection. Electrochemical sensors have also been fabricated, but these are less frequently reported, potentially due to the limited conductivity and cycling stability of MOFs. Notably, dual‐signal sensors mitigate background signals interference and enhance the accuracy of Hg2+ detection.…

Abstract Magnéli phase titanium suboxides (M‐TSOs) belong to a type of sub‐stoichiometric titanium oxides based on the crystal structure of rutile TiO2. They possess a unique shear structure, granting them exceptional electrical conductivity and corrosion resistance. These two advantages are crucial for electrode materials in electrochemistry, hence the significant interest from numerous researchers. However, the preparation of M‐TSOs is uneconomic due to high temperature reduction and other complex synthesis process, thus limiting their practical application in electrochemical fields. This review delves into the crystal structure, properties, and synthesis methods of M‐TSOs, and touches on their applications as electrocatalysts in wastewater treatment and electrochemical water splitting. Furthermore, it highlights the research challenges and potential future research directions in M‐TSOs.

Abstract Two units of highly stable luminescent triarylmethyl radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), were bridged by p‐phenylene linker. The photoluminescence quantum yield (PLQY) of PyBTM−PhPyBTM was at most 0.4 % in various organic solvents. Adding two mesityl groups on the terminals did not improve the PLQY. In the MesPyBTM−PhPyBTM−Mes, the mesityl group did not worked as an electron donor unlike the previously reported monoradical MesPyBTM. However, adding two n‐hexyl groups on the bridging p‐phenylene did greatly improve it, and the PLQY of the PyBTM−(Hex2Ph)PyBTM was 7 % in dichloromethane and acetone, and 12 % in poly(methyl methacrylate) (PMMA) film. Twisting p‐phenylene linker by hexyl groups hindered the π‐conjugation and suppressed the non‐radiative decay of the excited state.

Asymmetric catalytic carbene reactions have been well documented in the last few decades for the expeditious assembly of chiral molecules with structural diversity. However, the enantioselective construction of all-carbon quaternary centers remains a challenge in this area. In this review article, two types of asymmetric carbene reactions that beyond cyclopropanation, cyclopropenation, and Büchner reaction, have been summarized for the construction of all-carbon quaternary centers: 1) using carbene species as a 1C synthon that reacts with a trisubstituted prochiral center; 2) sequential installation of two different C-C bonds on the carbene position, which features a gem-difunctionalization reaction. Especially, the asymmetric metal carbene gem-dialkylation process, which has emerged as a practical and versatile method for the expeditious assembly of complex architectures from readily available chemical resources, is a complementary approach for the expeditious assembly of all-carbon quaternary centers.

Abstract This study conducts a thorough theoretical investigation of Thermally Activated Delayed Fluorescence (TADF) in phenothiazine‐based systems, examining ten molecular configurations recognized experimentally as TADF‐active. Employing Time‐Dependent Density Functional Theory (TD‐DFT), our analysis spans the investigation of singlet‐triplet energy gaps (ΔEST), spin‐orbit coupling, and excitation characteristics using Multiwfn. This approach not only validates the adherence to El Sayed's rule across these systems but also provides a detailed understanding of charge transfer dynamics, as visualized through heat maps. A significant aspect of our study is the exploration of different oxidation states of sulfur and site substitutions on phenothiazine. This systematic variation aims to identify additional TADF‐active compounds, drawing parallels with properties characterizing other known TADF emitters. Our investigation into Reverse Intersystem Crossing (rISC) rates and the analysis of dihedral angles in relation to ΔEST values offer nuanced insights into the TADF behaviours of these…

Abstract The nonheme iron dioxygenase deoxypodophyllotoxin synthase performs an oxidative ring‐closure reaction as part of natural product synthesis in plants. How the enzyme enables the oxidative ring‐closure reaction of (−)‐yatein and avoids substrate hydroxylation remains unknown. To gain insight into the reaction mechanism and understand the details of the pathways leading to products and by‐products we performed a comprehensive computational study. The work shows that substrate is bound tightly into the substrate binding pocket with the C7’−H bond closest to the iron(IV)‐oxo species. The reaction proceeds through a radical mechanism starting with hydrogen atom abstraction from the C7’−H position followed by ring‐closure and a final hydrogen transfer to form iron(II)‐water and deoxypodophyllotoxin. Alternative mechanisms including substrate hydroxylation and an electron transfer pathway were explored but found to be higher in energy. The mechanism is guided by electrostatic perturbations of charged residues in the second‐coordination sphere that prevent alternative pathways.

Abstract A divergent synthetic approach to access highly substituted indole scaffolds is illustrated. By virtue of a tunable electrochemical strategy, distinct control over the C‐3 substitution pattern was achieved by employing two analogous 2‐styrylaniline precursors. The chemoselectivity is governed by the fine‐tuning of the acidity of the amide proton, relying on the appropriate selection of N‐protecting groups, and assisted by the reactivity of the electrogenerated intermediates. Detailed mechanistic investigations based on cyclic voltametric experiments and computational studies revealed the crucial role of water additive, which assists the proton‐coupled electron transfer event for highly acidic amide precursors, followed by an energetically favorable intramolecular C−N coupling, causing exclusive fabrication of the C‐3 unsubstituted indoles. Alternatively, the implementation of an electrogenerated cationic olefin activator delivers the C‐3 substituted indoles through the preferential nucleophilic nature of the N‐acyl amides. This electrochemical approach of judicious…

Abstract In vitro, 19F NMR methodology is preferably selected as a complementary and straightforward method for unveiling the conformations, dynamics, and interactions of biological molecules. Its effectiveness in vivo has seen continuous improvement, addressing challenges faced by conventional heteronuclear NMR experiments on structured proteins, such as severe line broadening, low signal‐to‐noise ratio, and background signals. Herein, we summarize the distinctive advantages of 19F NMR, along with recent progress in sample preparation and applications within the realm of in‐cell NMR. Additionally, we offer insights into the future directions and prospects of this methodology based on our understanding.

Abstract Adducts between OsO 4 and Lewis bases exert a role in important oxidation processes such as epoxidation and dihydroxylation. It has been shown that the attractive interaction driving the formation of these adducts is a σ‐hole bond involving the metal as the electrophilic species; the term Osme Bond (OmB) was proposed for designating it. Here some new adducts between OsO 4 and various bases have been characterized through single crystal x‐ray diffraction (XRD) and computational studies (density functional theory, DFT), confirming the existence of a robust correlation between σ‐hole interaction energy and deformation of the tetrahedral geometry of OsO 4 . Also, some adducts formed by RuO 4 with nucleophiles were investigated computationally.

'Impossible' rotaxanes, which are constituted by interlocked components without obvious binding motifs, have attracted the interest of the mechanically interlocked molecules (MIMs) community. Within the synthetic efforts reported in the last decades towards the preparation of MIMs, some innovative protocols for accessing 'impossible' rotaxanes have been developed. This short review highlights different selected synthetic examples of 'impossible' rotaxanes, as well as suggests some future directions of this research area.