Chemistry - A European Journal最新文献

{"title":"Front Cover: Alkenyl Fluorosulfates—Expedient Partners for Palladium-Catalyzed Cross-Coupling Reactions","authors":"Vladyslav Hnativ,&nbsp;Serhii Aleksandrenko,&nbsp;Serhii Zhersh,&nbsp;Oleksandr O. Grygorenko","doi":"10.1002/chem.71393","DOIUrl":"https://doi.org/10.1002/chem.71393","url":null,"abstract":"<p><b>The Front Cover</b> showcases alkenyl fluorosulfates—reactive yet bench-stable building blocks for palladium-catalyzed cross-couplings, depicted as a blazing celestial body: high energy held in remarkable stability. These versatile reagents are readily prepared from carbonyl compounds and SO₂F₂, and participate in a variety of C–C and C–N bond-forming reactions—Suzuki, Sonogashira, Heck, Stille, Miyaura borylation, and Buchwald–Hartwig—opening access to previously underexplored regions of chemical space. For more details, read the Research Article by O. O. Grygorenko and co-workers (DOI: 10.1002/chem.71098). Artwork preparation by Emma Vilchynska.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.71393","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148811163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reversible Assembly and Disassembly of σ-Aromatic B₃ Rings.","authors":"Julian Krauß, Frederick Koch, Niels Karsten Paul Hecht, Elisabeth Kaifer, Hans-Jörg Himmel","doi":"10.1002/chem.71615","DOIUrl":"https://doi.org/10.1002/chem.71615","url":null,"abstract":"<p><p>Electron-deficient, planar oligoboron ring compounds fascinate due to their peculiar bonding properties (σ-aromaticity) and reactivity; however, the directed synthesis of such compounds is challenging. In this work we report on the reaction of cationic diboranes with boranes to give cationic, σ-aromatic B₃ ring compounds, with three-center-two-electron bond between the three boron atoms, being analogues of B₃H₈ ^-, but with opposite charge. Base-induced, reversible disassembly of the cationic B₃ ring leads back to cationic diboranes and borane adducts. Quantum-chemical calculations show that the thermodynamics of these reactions can be tuned by choice of the base. The reactions interconvert electron-deficient boron three-center bonds and electron-precise two-center bonds and disclose new synthetic access routes to cationic diboranes and σ-aromatic B₃ rings.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71615"},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148816855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vertically Aligned MoS₂/MXene Heterojunction as a Bifunctional Separator Coating for Suppressing Shuttle Effect and Enhancing Li⁺ Transport in Li-S Batteries.","authors":"Tao Wu, Yunxia Liu, Jie Chang, Ronghua Wang, Chaohe Xu","doi":"10.1002/chem.71592","DOIUrl":"https://doi.org/10.1002/chem.71592","url":null,"abstract":"<p><p>Lithium-sulfur batteries are considered one of the most promising next-generation energy storage systems owing to their high theoretical energy density and natural abundance of sulfur. However, their practical application is severely hampered by the polysulfide shuttle effect and sluggish conversion kinetics. Herein, a two-dimensional MoS₂/MXene heterojunction composite (MMS) is rationally designed via one-step hydrothermal growth of vertically aligned MoS₂ nanoflowers on conductive Ti₃C₂T_x MXene substrates. This unique architecture integrates the high conductivity of MXene with abundant catalytic edge sites of MoS₂, forming a tightly coupled heterointerface with 1T/2H mixed-phase MoS₂ that synergistically enables physical confinement, chemical adsorption, and electrocatalytic conversion of polysulfides. When employed as a functional coating on polypropylene separators, MMS@PP exhibits enhanced electrolyte wettability, high ionic conductivity (1.476 mS cm^-1), and a lithium-ion transference number of 0.49. Consequently, Li-S batteries incorporating MMS@PP deliver a high specific capacity of 1294.1 mAh g^-1 at 0.1 C with low polarization (161 mV), excellent rate capability (5 C), and outstanding cycling stability with 89.1% capacity retention after 100 cycles at 0.2 C. This work provides a rational heterojunction design strategy for developing multifunctional separators toward high-performance Li-S batteries.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71592"},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148816859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbazole-Substituted Heptazines With Hund Order of Excited Singlet/Triplet States for OLEDs.","authors":"Vyacheslav V Diev, Denis Kondakov, Xiaofan Ren, Yunlong Zou, Hjalti Skulason, Dong Gil Kim, Hong-Yeop Na, Glenn P A Yap","doi":"10.1002/chem.71621","DOIUrl":"10.1002/chem.71621","url":null,"abstract":"<p><p>Monomeric heptazines have recently attracted significant attention for applications in photocatalysis, optics, and organic electronics. Many heptazine derivatives are known to have high triplet energies that are close or even above their singlet energy (anti-Hund) that can be useful for applications in high efficiency organic light-emitting diodes (OLEDs). We report a convenient synthetic route to asymmetric bis-diarylamino carbazole-substituted heptazines obtained in high yields via sequential nucleophilic substitutions of trichloroheptazine. These materials were thoroughly characterized by NMR spectroscopy and single-crystal X-ray crystallography. Furthermore, their photophysical properties were systematically examined to determine the energies of excited singlet/triplet states. Photophysical measurements and high-level quantum chemical calculations demonstrate that bis-diarylamino carbazole-substituted heptazines are triplet wide bandgap materials that obey Hund's rule with T₁ lying lower in energy than S₁. Detailed analysis of the electronic structure of the excited states reveals that their nature differs significantly from that of anti-Hund heptazines with substantial localization/contribution of charge transfer character to carbazole and diarylamine moieties, which is responsible for Hund order of excited singlet/triplet states. Finally, application of bis-diarylamino carbazole-substituted heptazine 1 as wide bandgap host material for OLEDs does not interfere with triplet dynamics of emissive phosphor consistently with Hund order of excited singlet/triplet states.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71621"},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148816905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Breaking the Mold: Electrophilic Hydrophosphanation Emerges","authors":"Víctor Varela-Izquierdo,&nbsp;Janeth Navarro,&nbsp;Judit Cano-Asensio,&nbsp;José A. López,&nbsp;Cristina Tejel","doi":"10.1002/chem.71103","DOIUrl":"10.1002/chem.71103","url":null,"abstract":"<p>Herein, we report an unprecedented mechanism for the catalytic hydrophosphanation of olefins in which the key step involves an electrophilic hydride attack on the olefin rather than the classical nucleophilic addition of a phosphanido ligand. This mechanistic paradigm redefines the fundamental reactivity of P–H compounds with C═C bonds under catalytic conditions. The dichotomy between electrophilic and nucleophilic pathways has been elucidated through DFT calculations and experimental kinetic isotope effect (KIE) measurements. We also demonstrate that this mechanistic pattern is applicable to both electronically activated and non-activated olefins, as well as to non-symmetric olefins. In a parallel finding, we have identified a novel reactivity mode of hydrido-phosphanido species, in which the phosphanido moiety engages in an intramolecular attack on a tethered olefin to afford a previously unreported diphosphaenolate. This transformation, due to the amphiphilic behavior of complex [Rh(Tp)(PHPh₂)(H)(PPh₂)], expands the chemical space accessible through hydrophosphanation-derived pathways.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.71103","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147939503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Many Facets of Metal-Binding Peptides","authors":"Emilie Mathieu,&nbsp;Christelle Hureau","doi":"10.1002/chem.71045","DOIUrl":"10.1002/chem.71045","url":null,"abstract":"<div>\u0000 \u0000 <p>This virtual special issue provides an overview of recent advances in the field of metal-binding peptides, which covers a broad range of thematics ranging from catalysis to health and environment. In this editorial, guest editors E. Mathieu and C. Hureau introduce its content.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147925038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalyst-Free Cyanation of Arenes by Acetonitrile in a Plasma–Liquid Microreactor","authors":"Pierre Dedieu,&nbsp;Gabriel Morand,&nbsp;Stéphanie Ognier,&nbsp;Alain Favre-Réguillon,&nbsp;Michael Tatoulian","doi":"10.1002/chem.71101","DOIUrl":"10.1002/chem.71101","url":null,"abstract":"<p>A catalyst-free direct C-H cyanation of arenes was performed in continuous flow by treating aromatic substrates in acetonitrile with an argon plasma in a gas–liquid microreactor under ambient conditions. The reactivity of the different radicals generated through plasma activation of acetonitrile was probed using benzene as a model substrate, producing benzonitrile in a 25% yield. Mechanistic insights derived from kinetic modeling and isotopic labeling experiments enabled the proposal of a reaction pathway accounting for the formation of the main nitrile products. Expanding the substrate scope demonstrated consistent nitrile formation aligned with the mechanistic hypothesis. This catalyst-free direct C-H cyanation of arenes using an accessible and low-toxicity nitrile source highlights the promising role of plasma activation as an alternative tool for organic transformations.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.71101","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147924973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aperture-Controlled Cs+ Uptake/Release Kinetics and Extremely Short Cs+–π Contact in Open-Cage Cobalt(III) Metallocryptands","authors":"Shigehisa Akine,&nbsp;Sachiko Yano","doi":"10.1002/chem.71063","DOIUrl":"10.1002/chem.71063","url":null,"abstract":"<div>\u0000 \u0000 <p>Cage-shaped molecules with an internal cavity provide platforms for molecular recognition. However, systematic control over guest exchange kinetics remains limited. Here, we report a series of cobalt(III) metallocryptands in which guest uptake/release rates are tuned by steric modulation of the cage apertures. The open-cage metallocryptands LCo₃A₆, bearing monoamine ligands (A = MeNH₂, EtNH₂, PrNH₂) of different steric bulk, were synthesized and their Cs⁺ uptake/release behavior was investigated. The guest exchange rates depend strongly on the coordinated amine ligands, spanning timescales from 6.5 s to 24 min, which are significantly faster than those of the corresponding closed-cage analogue, LCo₃(hda)₃ (hda = 1,6-hexanediamine). X-ray crystallographic analyses confirmed that the Cs⁺ ion is completely encapsulated within the cavity to form robust cation-in-cation structures, despite the tricationic nature of the cryptand host. These analyses further revealed unusually short Cs⁺–π distances in the range of 2.98–3.04 Å, significantly shorter than the previously reported range of 3.3–3.6 Å, due to geometrical constraints imposed by the rigid metallocryptand framework with a 6.0 Å π–π spacing. Structural comparisons demonstrated that the steric bulk of the amine ligands modulates the cage aperture sizes, accounting for the observed kinetic trends.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147872521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"1-Nitro-7-Donor Functionalized Perylenediimides: Synthesis, Photophysical Properties, Redox Behavior, and Nanosecond Transient Studies","authors":"Mohd Wazid,&nbsp;Xi Chen,&nbsp;Peiwen Jiang,&nbsp;Jianzhang Zhao,&nbsp;Rajneesh Misra","doi":"10.1002/chem.71044","DOIUrl":"10.1002/chem.71044","url":null,"abstract":"<div>\u0000 \u0000 <p>A set of push–pull donor substituted nitro-perylenediimide (NO₂-PDI)-based derivatives <b>NPDI 1</b>–<b>4</b> were designed and synthesized via nitration reaction of the mono-brominated-PDI (Br-PDI) followed by Pd(II)-catalyzed Sonogashira cross–coupling reaction in good yields. The nitro group was substituted at the bay position of the PDI-NO₂, and a variety of donors (phenothiazine (PTZ), carbazole(CBZ), and <i>N,N</i>-dimethylaniline(NND) were functionalized on the other bay side. The photophysical, electrochemical, spectroelectrochemical, computational calculations, and nanosecond transient absorption (ns-TA) studies were performed on the synthesized derivatives <b>NPDI 1</b>–<b>4</b>. The photophysical properties of <b>NPDI 2</b>–<b>4</b> exhibit absorption in the NIR region due to strong push–pull interaction, resulting in stabilized LUMO energy levels to a greater extent. The electrochemical study reveals that the redox potentials of <b>NPDI 1</b>–<b>4</b> derivatives shifted toward the anodic side due to the strong electron-withdrawing nature of the NO₂-PDI moiety. The spectroelectrochemical analysis revealed the absorption spectra shifted toward the bathochromic region during the reduction cycles, while a hypochromic shift occurred during the oxidation cycles. Nanosecond transient absorption spectral studies show that for the compounds containing strong electron donors (such as PTZ), either a short triplet state lifetime (<i>τ</i>_T = 0.47 µs for <b>NPDI2</b>) or no ISC was observed (<b>NPDI4</b>). For the compounds with moderate or no electron donor attached in the molecular structure, long triplet state lifetimes were observed (<i>τ</i>_T = 86.9 µs for <b>NPDI1</b> and <i>τ</i>_T = 47.8 µs for <b>NPDI3</b>). For the compounds lacking ISC ability, an intermolecular triplet photosensitizing method, and long triplet state lifetimes were observed (<i>τ</i>_T = 46 µs for <b>NPDI4</b>).</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147866085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sunlight-Driven Green Synthesis of Platinum Nanoparticles From Double-Vacancy Halide Perovskite Precursors for Methanol Reforming","authors":"Kevin Mego,&nbsp;Saray Chacón-Ruiz,&nbsp;Pedro Ruiz-Campos,&nbsp;Herme G. Baldoví,&nbsp;Pedro Atienzar","doi":"10.1002/chem.202503192","DOIUrl":"10.1002/chem.202503192","url":null,"abstract":"<p>The development of synthetic procedures for preparing metal nanoparticles with controlled size using sunlight opens new avenues toward more sustainable methods with lower energy consumption. Herein, we propose the use of double-vacancy halide perovskites as precursors for engineering highly crystalline and small platinum nanoparticles (&lt; 3 nm) under simulated sunlight irradiation, using low concentration of methanol as sacrificial agent at room temperature. The formation of Pt NP was dependent on the methanol concentration impacting in the final Pt particle size distribution and time formation. After purification, this narrow sized Pt NP were employed for the methanol reforming reaction, showing excellent activity after 4 h and high selectivity toward hydrogen production (4.18 mmol·h⁻¹ of H₂), along with other carbon products such as CO (2.26 mmol·h⁻¹), CH₄ (0.54 mmol·h⁻¹), CO₂ (0.28 mmol·h⁻¹), and C₂ species (0.17 mmol·h⁻¹).</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 32","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202503192","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147872618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}