Habib Assy, Dr. Uttam K. Mishra, Tom Rösler, Dr. Raman Khurana, Prof. N. Gabriel Lemcoff, Prof. Ofer Reany
{"title":"Cover Feature: Stereospecific Radical Bromination of β-Aryl Alcohols with Thiourea Additives Through A Serendipitous Discovery of A 1,2-Aryl Migration (Chem. Eur. J. 19/2025)","authors":"Habib Assy, Dr. Uttam K. Mishra, Tom Rösler, Dr. Raman Khurana, Prof. N. Gabriel Lemcoff, Prof. Ofer Reany","doi":"10.1002/chem.202581903","DOIUrl":"https://doi.org/10.1002/chem.202581903","url":null,"abstract":"<p><b>The Cover Feature</b> shows a unique radical mechanism that allows fully stereoretentive bromination of beta-aryl alcohols under very mild conditions by using <i>N</i>-bromo-succinimide (NBS) and substoichiometric thiourea. More information can be found in the Research Article by N. G. Lemcoff O. Reany and co-workers (DOI: 10.1002/chem.202403831).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581903","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749506","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}
Marina Tsigkou, Eleni Nikoli, Dr. Ioanna K. Sideri, Michalis Kardaras, Dr. Hiram Joazet Ojeda Galvan, Prof. Mildred Quintana, Dr. Nikos Tagmatarchis
{"title":"Front Cover: Electronic Interactions in Coulombic Associated Photoactive Macrocycles to Chemically Modified MoS2 Nanosheets (Chem. Eur. J. 19/2025)","authors":"Marina Tsigkou, Eleni Nikoli, Dr. Ioanna K. Sideri, Michalis Kardaras, Dr. Hiram Joazet Ojeda Galvan, Prof. Mildred Quintana, Dr. Nikos Tagmatarchis","doi":"10.1002/chem.202581901","DOIUrl":"https://doi.org/10.1002/chem.202581901","url":null,"abstract":"<p><b>The Front Cover</b> illustrates the electrostatic interactions between MoS₂ and three chromophores depicted as the loosely attached leaves of a blooming flower. At the core, MoS₂ acts as the central pistil, serving as the foundation for charge and energy exchange. Like leaves harvest sunlight in nature, the chromophores interact with MoS₂ in a reversible yet influential manner, shaping the photophysical behavior within each nanoensemble. The fluid background symbolizes both the dispersion nature of these materials and the dynamic, noncovalent forces that guide their assembly. More information can be found in the Research Article by N. Tagmatarchis and co-workers (DOI: 10.1002/chem.202404746).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581901","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749380","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}
Yuepeng Liu, Fang Lei, Tingting Li, Siyu Wang, Prof. Dr. Yi Li
{"title":"Cover Feature: Noble-Metal-Free Electrocatalysts for Selective Hydrogen Peroxide Generation via Oxygen Reduction Reaction (Chem. Eur. J. 19/2025)","authors":"Yuepeng Liu, Fang Lei, Tingting Li, Siyu Wang, Prof. Dr. Yi Li","doi":"10.1002/chem.202581902","DOIUrl":"https://doi.org/10.1002/chem.202581902","url":null,"abstract":"<p><b>Hydrogen peroxide</b> is a versatile chemical used in various fields; however, traditional synthesis methods have environmental and safety issues. The 2e<sup>−</sup> ORR method is gaining attention for its safety, environmental friendliness, and cost effectiveness. In their Review (DOI: 10.1002/chem.202404164), Y. Li and co-workers discuss recent progress in non-precious-metal materials for efficient H<sub>2</sub>O<sub>2</sub> preparation by electrocatalysis, highlighting their advantages and future trends.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581902","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749381","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}
Yaxi Wang, Kaile Dou, Junliang Liu, Lei Zhang, Lu Hu, Siping Pang
{"title":"A Reversible Nitroamino-Based Switch Modulates Hydrogen-Bonding Networks in Energetic Materials.","authors":"Yaxi Wang, Kaile Dou, Junliang Liu, Lei Zhang, Lu Hu, Siping Pang","doi":"10.1002/chem.202500884","DOIUrl":"https://doi.org/10.1002/chem.202500884","url":null,"abstract":"<p><p>The regulation of hydrogen-bonding networks in molecular switches is critical for adaptive materials. However, most of the reported molecular switches do not are not capable of modulating hydrogen-bonding networks in energetic materials, limiting their use in high-demand applications such as energetic systems. In this work, the first high-energy nitroamino-based molecular switch is reported. It can control the complex hydrogen bonding systems of energetic materials by reversible cycling for property modulation. Through alkali-acid stimulation, the nitroamino-based switch undergoes dynamic transitions, which reconfigure H-bond networks and separate twin crystals (in X-ray verification). Supported by crystallography and theorical modeling (e.g., the density of states), this switching mechanism modulates molecular planarity (Δθ>60°) and optimizes the energy-stability balance, obtaining a compound 6-β with comprehensive properties comparable to classical explosives (e.g., RDX and HMX). By linking hydrogen-bonding engineering and energetic materials science through the nitroamino-based molecular switch, it facilitates superior energetic compounds that can be applied to defense equipments. In addition, our work establishes the nitroamino-based switch as a generalized tool for molecular engineering, bridging dynamic hydrogen-bonding control and self-assembly materials design.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500884"},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750466","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}
Dr. Masashi Uebe, Koshi Yoshida, Prof. Dr. Shu Seki, Prof. Dr. Akihiro Ito
{"title":"Cover Feature: Radical Cation of Tris(Triarylamine) Connected through 1,2,3-Benzenetriyl Bridge: A Three-Redox-Center Organic Mixed-Valence System (Chem. Eur. J. 19/2025)","authors":"Dr. Masashi Uebe, Koshi Yoshida, Prof. Dr. Shu Seki, Prof. Dr. Akihiro Ito","doi":"10.1002/chem.202581904","DOIUrl":"https://doi.org/10.1002/chem.202581904","url":null,"abstract":"<p><b>The Cover Feature</b> depicts the molecular structure of a tris(triarylamine) radical cation, in which three triarylamine redox-active centers are connected in a side-by-side fashion via a 1,2,3-benzenetriyl bridging unit, and the generated mixed-valence state induces intramolecular electron transfer, like an “electronic” bird flying around the molecule. The process was elucidated by a combination of experimental (optical absorption and ESR spectroscopy) and theoretical (density functional theory calculations) analyses. More information can be found in the Research Article by S. Seki, A. Ito and co-workers (DOI: 10.1002/chem.202404436).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581904","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749507","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-Bond-Mediated Polymers: Strengthening, Toughening, and Stabilizing Effects.","authors":"Xiaokong Liu, Guangwen Men, Wenwen Niu","doi":"10.1002/chem.202500674","DOIUrl":"https://doi.org/10.1002/chem.202500674","url":null,"abstract":"<p><p>Traditionally, the design and synthesis of polymers have centered on engineering their covalent chain or network structures. However, noncovalent interactions between polymer chains can influence the properties of polymers to a degree comparable to or even greater than their covalent structures. Therefore, shifting the focus of polymer design from covalent structure engineering to noncovalent interaction modulation represents a new paradigm for polymer innovation. This Concept article summarizes our recent advances in H-bond-mediated polymers (HBMPs), fabricated by meticulously tuning the interchain/intersegment H-bonding interactions, in conjunction with rational design of the covalent polymer chain or network structures. We demonstrate that H-bond-mediated assembly provides an effective strategy to fabricate new polymers with unprecedented properties and sustainability, using commodity polymers as building blocks. Importantly, the synergy of multivalence cooperativity and dynamic nature of the H-bonding interactions in HBMPs can reconcile the intrinsic trade-off between mechanical strength and toughness of polymers, achieving both superhigh strength and superhigh toughness. Moreover, optimizing multivalence cooperativity can make the H-bonded crosslinks exhibit a covalent crosslinking effect, offering thermoset-like stability while preserving thermoplastic-like recyclability. The concept of HBMPs can be extended to noncovalent-bond-mediated systems, opening new avenues for polymer innovation and expanding the potential for creating functional and sustainable materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500674"},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750611","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":"A Cytotoxic Indazole-based Gold(III) Carboxamide Pincer Complex Targeting DNA through Dual Binding Modes of Groove Binding and Alkylation.","authors":"Rufaro Razuwika, Sheldon Sookai, Ruth Aronson, Mandeep Kaur, Orde Q Munro","doi":"10.1002/chem.202404345","DOIUrl":"https://doi.org/10.1002/chem.202404345","url":null,"abstract":"<p><p>Gold(III) complexes have garnered increasing attention in drug delivery due to their structural and mechanistic similarities to cisplatin. This study investigates an indazole-based gold(III) carboxamide pincer complex, AuL, for its potential as an anticancer agent. Speciation analysis at physiological pH revealed that AuL predominantly exists as a neutral chlorinated species. The complex exhibited strong cytotoxicity against the MCF-7 breast cancer cell line, with an impressive IC50 value of 9 µM, while showing no significant activity against the HT-29 colon cancer cell line. Comprehensive analysis using electrophoresis, viscometry, UV-Vis, CD, LD spectroscopy, and biomolecular simulations demonstrated that AuL binds to DNA via a dual mechanism: minor groove binding and alkylation, with binding constants Ka1 =1.48 x109 M-1 and Ka2 = 6.59 x105 M-1, respectively. Our data indicates that AuL initially binds to the minor groove of DNA, at which point nucleobase substitute the Cl ion resulting in AuL alkylating to DNA In conclusion, the dual binding mode of AuL with DNA underscores its potential as a promising anticancer agent, which may open new avenues for drug discovery and development of metal-based therapeutics.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404345"},"PeriodicalIF":3.9,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750437","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}
Ming Chen, Yunjiao Peng, Junrui Zhang, Wei Liu, Xunshan Liu
{"title":"Reversible Quinoid-Diradical Inter-conversion in Single-Molecule Junctions.","authors":"Ming Chen, Yunjiao Peng, Junrui Zhang, Wei Liu, Xunshan Liu","doi":"10.1002/chem.202500921","DOIUrl":"https://doi.org/10.1002/chem.202500921","url":null,"abstract":"<p><p>profound understanding of the reversible regulation mechanisms among multiple redox states of organic molecules is essential for further development of molecular switching devices. In this study, an oligo-aniline derived quinoidal molecular wire was designed and synthesized. The reversible inter-conversion processes between its initial (quinoidal) and protonated (diradical) states were comprehensively investigated with optical measurements, and the EPR experiments confirmed the formation of radical species upon protonation. The single-molecule charge transport properties were then investigated using scanning tunneling microscopy break junction (STM-BJ) technique. It was found that the molecular wire O-ANI can serve as a reversible molecular switching process with around 6.5-fold conductance variation through acid/base adjustments. Additionally, theoretical analyses elucidated the mechanism of the quinoidal-diradical inter-conversion. The enhanced comprehension of the reversible quinoidal-diradical inter-conversion at the single-molecule level provides new strategies for advancing the molecular switching materials and devices.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500921"},"PeriodicalIF":3.9,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750619","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":"Control of Chemo-Selectivity via Alcohol Affected Kinetics in Cu-Hydroxylamine Catalyzed Aerobic Oxidation of Mesitol.","authors":"Jiaxin Liu, Yongtao Wang, Jia Yao, Haoran Li","doi":"10.1002/chem.202501032","DOIUrl":"https://doi.org/10.1002/chem.202501032","url":null,"abstract":"<p><p>Chemo-selectivity control is a critical challenge in aerobic C-H oxidations, particularly in preventing overoxidation. In this work, we present an alcohol-tunable strategy to control the oxidation degree of CuCl2/NH2OH·HCl-catalyzed mesitol oxidation in alcohols. In tBuOH, the reaction efficiently yields the aldehyde product with high selectivity, whereas in MeOH, the ether intermediate turned to be the predominant product. Further kinetic analysis and mechanistic studies revealed that the reactivity is driven by the in-situ formation of protonated alkyl nitrate ([RON(O)OH]+), highlighting the critical role of ROH solvents. The differing responses of mesitol and the ether intermediate to the reaction conditions result in distinct kinetics across different alcohols, enabling precise control over the final products. These findings provide mechanistic insights into the origins of alcohol-dependent chemo-selectivity and pave the way for advancing protocols for selectivity control.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501032"},"PeriodicalIF":3.9,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750472","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}
Rebecca Salthouse, Amit Sil, Piotr Pander, Fernando Dias, J A Gareth Williams
{"title":"Molecular Rectangles Featuring Two Parallel NCN-Coordinated Platinum Units: Enhancing Near-infrared Emission through Excimer Formation.","authors":"Rebecca Salthouse, Amit Sil, Piotr Pander, Fernando Dias, J A Gareth Williams","doi":"10.1002/chem.202500834","DOIUrl":"https://doi.org/10.1002/chem.202500834","url":null,"abstract":"<p><p>New macrocyclic molecules are described that incorporate Pt(NCN) units on opposite edges of a rectangular structure, with xanthene units constituting the other two sides. Here, NCN represents a cyclometallating tridentate ligand based on 2,6-di(2-pyridyl)benzene or its pyrimidine analogue. The complexes display strong photoluminescence peaking in the near-infrared region of the spectrum in solution (λmax up to 761 nm). Photophysical data and DFT calculations indicate that the emission arises from \"intramolecular excimers\" - triplet excited states that form when the two Pt(NCN) units within the molecule are brought into close proximity to interact interfacially. In doped polymers, the necessary molecular distortion is inhibited, but related excited states that emit in a similar region can still form through intermolecular interactions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500834"},"PeriodicalIF":3.9,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750616","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}