Chemistry - A European Journal最新文献

{"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":"Anchoring Monolayer TiOx Nanosheets on Gold Nanoparticles Enhances Catalytic Activity for CO Oxidation Depending on the Type of Support","authors":"Nayu Hamada,&nbsp;Akihiro Nakayama,&nbsp;Riku Suzuki,&nbsp;Kosei Arata,&nbsp;Norihito Sakaguchi,&nbsp;Hiroya Ishikawa,&nbsp;Toru Murayama,&nbsp;Tetsuya Shimada,&nbsp;Shinsuke Takagi,&nbsp;Tamao Ishida","doi":"10.1002/chem.71123","DOIUrl":"10.1002/chem.71123","url":null,"abstract":"<p>Catalytic performance of supported gold catalysts is governed by the contact structure between Au nanoparticles (NPs) and reducible metal oxides. In this study, we constructed an Au–TiO_x interface by decorating supported Au NPs with monolayer titania nanosheets (TNS). We report a support-dependent formation of the interface between Au and TiO_x thin overlayer. For Au/SiO₂, TNS adsorption followed by calcination significantly enhanced CO oxidation activity. In contrast, for Au/CeO₂, TNS adsorption without calcination markedly improved the activity. Spectroscopic analyses revealed that cationic Au and Ti³⁺ species increased after TNS adsorption for Au/CeO₂ and the subsequent calcination for Au/SiO₂, respectively, suggesting the formation of Au–TiO_x interface. X-ray photoelectron spectroscopy (XPS) showed that TNS adsorption on CeO₂ induced a slight increase in Ce³⁺ species, consistent with Ce–O–Ti anchoring via interaction between surface Ti–OH and Lewis acidic Ce⁴⁺ sites. The surface reaction between TNS and redox-active CeO₂ gives Au–TiO_x contact structures, whereas nonreducible SiO₂ requires calcination. Moreover, the TiO_x overlayer derived from TNS was more oxygen-deficient than that obtained by impregnation of Ti species. This work demonstrates that the use of monolayer TNS is advantageous for the formation of active Au–TiO_x interface and rich oxygen vacancies.</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.71123","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147925053","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":"Hydrogen-Bonded Chemical Energy Storage Mechanism of Ruthenium Oxide-Coated Porous Silicon Nanowires","authors":"Bing Bai,&nbsp;Xiaofeng Zhang,&nbsp;Peiao Lu,&nbsp;Jiakun Luo,&nbsp;Wei Xu,&nbsp;Yingqi Li,&nbsp;Jinyu Wu,&nbsp;Kui-Qing Peng","doi":"10.1002/chem.71116","DOIUrl":"10.1002/chem.71116","url":null,"abstract":"<div>\u0000 \u0000 <p>Aqueous ammonium ion-based (NH₄⁺) hybrid supercapacitors (AAHSCs) are attracting great attention because of their excellent electrochemical performance and environmental friendliness. Silicon nanowires have attracted extensive attention due to their unique physical/chemical properties that make them appealing in emerging energy conversion and storage applications. In this work, porous silicon nanowires (p-SiNWs) were used as scaffolds to coat RuO₂ nanospheres by hydrothermal treatment. The as-prepared RuO₂ nanospheres completely encapsulate the silicon nanowires, providing abundant active sites for NH₄⁺ attachment. The O-atoms in RuO₂ combine with NH₄⁺ to form hydrogen bonds (H-bonds), which greatly improve the electrochemical performance by promoting the charges transport through H-bonds formation/breaking during charging/discharging. In comparison with pure p-SiNWs, RuO₂@p-SiNWs electrode exhibits a higher areal capacitance of 128 mF/cm² at 0.1 mA. The capacitor is prepared with RuO₂@p-SiNWs as the cathode and activated carbon (AC) as the anode, separated by (NH₄)₂SO₄ electrolyte, achieving an aerial capacitance of 35.9 mF/cm² at the current of 0.2 mA. The proposed concept opens new avenue for developing advanced high-energy-density cathode materials for AAHSCs.</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":"147872451","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":"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":"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}