Chemistry - A European Journal最新文献_第10页

Host Cavities Enhance the Photocatalytic Conversion of α-Terpinene to Ascaridole Under Visible-Light Irradiation. 宿主空腔增强可见光照射下α-萜烯光催化转化为蛔虫素。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-09-02 DOI: 10.1002/chem.202502113

Mawgan U Main, Dominic Taylor, Leonardo Amicosante, John M Tobin, Callum M S Jones, Jose Marques-Hueso, Laura J McCormick McPherson, Simon J Teat, David Ellis, Martin J Paterson, Filipe Vilela, Scott J Dalgarno

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Rational Design of Cationic Silyl Lewis Acids. 阳离子硅基路易斯酸的合理设计。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-09-02 DOI: 10.1002/chem.202502431

Corinna Girschik, Saskia Rathjen, Lina Möllmann, Gülsera Eruçar, Marc Schmidtmann, Thomas Müller

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An Unusual Activity of Conformationally Restricted Naphthalene Peri-Dichalcogenides in the Reduction of Nitro and Azide Groups. 构象受限的萘环二硫族化合物在还原硝基和叠氮基中的异常活性。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-09-01 DOI: 10.1002/chem.202502017

Debasish Giri, Ekta Chauhan, Sourav Das, Govindasamy Mugesh

{"title":"An Unusual Activity of Conformationally Restricted Naphthalene Peri-Dichalcogenides in the Reduction of Nitro and Azide Groups.","authors":"Debasish Giri, Ekta Chauhan, Sourav Das, Govindasamy Mugesh","doi":"10.1002/chem.202502017","DOIUrl":"https://doi.org/10.1002/chem.202502017","url":null,"abstract":"Rigid and conformationally restricted dichalcogenides based on 1,8-naphthyl system have attracted significant interest as electron donors in charge transfer complexes and organic electrode materials. Recently, naphthalene-1,8-peri-diselenides have been shown to mimic the function of two major selenoenzymes - iodothyronine deiodinase (Dio) and glutathione peroxidase (GPx) - mainly through two-electron redox processes involving deiodination of thyroid hormones and thiol-mediated reduction of hydrogen peroxide, respectively. Herein, we report that naphthalene-1,8-peri-dichalcogenides can mediate a six-electron reduction of organic nitro compounds to produce the corresponding primary amines at physiologically relevant temperature (37 °C) using water as the solvent. The stepwise reduction process is highly dependent on the nature of the chalcogen atom present at the peri-positions of the naphthyl ring. While no reduction was observed with the disulfide, the selenenyl sulfide mediated a four-electron reduction of the nitro group to the corresponding hydroxylamine. The diselenide and ditelluride reduced the nitro groups all the way to amines through six-electron transfer. The diselenides also mediated the reduction of various aromatic azides to the corresponding primary amines.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02017"},"PeriodicalIF":3.7,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937128","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}

引用次数: 0

New ESIPT-Dyes of Record Capacity to Fluorescence Detection of H-Bond Donor and Acceptor Molecules, Including Local Water Concentration. 新型esipt染料对氢键供体和受体分子（包括局部水浓度）的荧光检测能力创记录。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-09-01 DOI: 10.1002/chem.202502388

Anton Hlavin, Vadym Dudko, Andrii Malashchuk, Ihor Komarov, Vasyl Pivovarenko

{"title":"New ESIPT-Dyes of Record Capacity to Fluorescence Detection of H-Bond Donor and Acceptor Molecules, Including Local Water Concentration.","authors":"Anton Hlavin, Vadym Dudko, Andrii Malashchuk, Ihor Komarov, Vasyl Pivovarenko","doi":"10.1002/chem.202502388","DOIUrl":"https://doi.org/10.1002/chem.202502388","url":null,"abstract":"5-Substituted 3-hydroxychromones (3-HCs) are challenging to synthesize but are of significant interest as fluorescent labels. This is primarily due to the pronounced modulation of their fluorescence by surrounding molecules, a consequence of the 5-substituent's proximity to the negative pole of the molecular dipole. The newly synthesized derivatives of 3-hydroxy-2-(4-methoxyphenyl)-4-oxo-4H-chromene-5-carboxylic acid exhibit unique fluorescence behaviors. Their color of emission is highly sensitive to the solvation environment and is strongly influenced by the nature of the functional group introduced at position 5. Notably, the fluorescence of acid demonstrates inhibition of ESIPT (excited-state intramolecular proton transfer) in both neutral and H-bond donor solvents, a phenomenon not previously observed in 3-HCs. Furthermore, investigated dye stands out as the first 3-HC compound whose fluorescence responds to the H-bond acceptor capacity of the environment, particularly in mildly acidic conditions (below pH 6). In contrast, methyl ester and glycine amide of key acid are responsive to the H-bond donor properties of their surroundings-a feature especially relevant in biological systems, where local water concentration plays a critical role. Thus, the derivatives such as N-terminal or lysine-labeled peptides incorporating these dyes can serve as valuable tools for investigating peptide-DNA, peptide-lipid, and other biomolecular interactions for the selected location of peptide.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02388"},"PeriodicalIF":3.7,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937030","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}

引用次数: 0

A Strategic Advance from Pincer Complexes to Hexadentate-Co(III) Catalyst for Metal-Ligand Cooperative Activation of Primary Alcohols to Access Highly Functionalized Pyrimidines. 从钳形配合物到六齿体co （III）催化剂对伯醇金属-配体协同活化获得高功能化嘧啶的策略进展。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-30 DOI: 10.1002/chem.202502258

Prashant Kukreti, Yutaka Hitomi, Kaushik Ghosh

{"title":"A Strategic Advance from Pincer Complexes to Hexadentate-Co(III) Catalyst for Metal-Ligand Cooperative Activation of Primary Alcohols to Access Highly Functionalized Pyrimidines.","authors":"Prashant Kukreti, Yutaka Hitomi, Kaushik Ghosh","doi":"10.1002/chem.202502258","DOIUrl":"https://doi.org/10.1002/chem.202502258","url":null,"abstract":"In this report, we present a sustainable, eco-friendly, practical, and cost-effective one-pot three-component reaction for the synthesis of a diverse library of highly substituted pyrimidines from amidines, primary alcohols, and aromatic ketones, catalyzed by a cobalt(III) complex. The well-defined cobalt(III) complex [Co(III)BPMAP-O]ClO4 is derived from a redox-active phosphine-free, pentadentate mono-carboxamide ligand (BPMAP-H), and is formed in situ from various cobalt(II) sources, including CoCl2·6H2O, CoBr2, Co(NO3)2·6H2O, Co(OAc)2·4H2O via oxygen activation. Using aromatic ketones and benzyl alcohols, a wide range of 2,4,6-trisubstituted pyrimidines (TriPym) and 2,4,5,6-tetrasubstituted pyrimidines (TetraPym) were synthesized (119 examples) in isolated yields of up to 93%. The catalytic system is also applicable to aliphatic ketones and aliphatic primary alcohols, affording 31 additional examples with yields of up to 92%. Control experiments and DFT calculations support a plausible mechanism involving dehydrogenation of the alcohols through a metal-ligand cooperative pathway.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02258"},"PeriodicalIF":3.7,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937120","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}

引用次数: 0

A Bichromophoric Triazatruxene Tetrad as a Highly Tunable Multicolor Emitter and Its Application in OLEDs. 双色性三氮杂蒽四元高可调谐多色发射体及其在oled中的应用。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-30 DOI: 10.1002/chem.202501992

Lars Vogelsang, Muhammad Irfan Haider, Kai Vogelsang, Tobias Seewald, Azhar Fakharuddin, Niklas Bauch, Gabriel Maier, Katharina L Deuter, Tobias Birk, Mikhail Fonin, Lukas Schmidt-Mende, Rainer F Winter

{"title":"A Bichromophoric Triazatruxene Tetrad as a Highly Tunable Multicolor Emitter and Its Application in OLEDs.","authors":"Lars Vogelsang, Muhammad Irfan Haider, Kai Vogelsang, Tobias Seewald, Azhar Fakharuddin, Niklas Bauch, Gabriel Maier, Katharina L Deuter, Tobias Birk, Mikhail Fonin, Lukas Schmidt-Mende, Rainer F Winter","doi":"10.1002/chem.202501992","DOIUrl":"https://doi.org/10.1002/chem.202501992","url":null,"abstract":"We report on the new star-shaped triazatruxene (TAT) tetrad 1, where three peripheral TAT moieties connect to a central TAT through propargylic spacers. The insulating nature of the linkers results in separate, partially overlapping blue and yellow-orange emissions from the peripheral and central TATs. This renders 1 a multicolor emitter, whose emission color can be tuned by the choice of the excitation wavelength and the solvent. In frozen solution, dual fluorescence emission from the two different types of TATs is complemented by dual phosphorescence with radiative lifetimes in the range of seconds. Organic light-emitting devices (OLEDs) constructed with 1 as the emissive layer achieved a peak irradiance of 5.87 µW/nm/m2 at 580 nm at an operation voltage of 6.7 V. Remarkably, the emission color of the electroluminescence can be varied from yellow over different hues of orange to red or even to near infrared (NIR) emission, depending on the applied voltage. Tetrad 1 is also redox-active, indicating that 1 may simultaneously serve as a hole conductor and emitter. Its oxidized forms are panchromatic absorbers from the near UV to the NIR due to intra- and inter-TAT charge-transfer (CT) absorptions.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01992"},"PeriodicalIF":3.7,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937090","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}

引用次数: 0

Electrochemical and Photoelectrochemical Transformations of Thioamides. 硫酰胺的电化学和光电化学转化。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-30 DOI: 10.1002/chem.202502278

Zuzanna Bieńkowska, Ijaz Khan, Magdalena Skompska, Katarzyna Rybicka-Jasińska

引用次数: 0

Speciation and Luminescence of a Binuclear Lanthanide Complex Bearing an Aminophenolate Chromophore. 含氨基酚酸酯发色团的双核镧系配合物的形成和发光。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-29 DOI: 10.1002/chem.202502305

Villads R M Nielsen, Charlie H Simms, Daniel Kovacs, Matthew F Allen, Matthew J Langton, Stephen Faulkner, Thomas Just Sørensen

{"title":"Speciation and Luminescence of a Binuclear Lanthanide Complex Bearing an Aminophenolate Chromophore.","authors":"Villads R M Nielsen, Charlie H Simms, Daniel Kovacs, Matthew F Allen, Matthew J Langton, Stephen Faulkner, Thomas Just Sørensen","doi":"10.1002/chem.202502305","DOIUrl":"https://doi.org/10.1002/chem.202502305","url":null,"abstract":"Lanthanide(III) complexes show diverse speciation in solution. Here, the photophysical properties and speciation in solution of binuclear lanthanide complexes bearing an aminophenolate chromophore that reversibly bind to both metal centers were determined. The aminophenolate can reversibly bind to both lanthanide ions in a pH dependent manner. Above pH 3 the phenolate moiety remains deprotonated and the lanthanide complexes exhibit very high kinetic stability, however, protonation of the amino group modulates the luminescence intensity without changing the luminescence lifetime of the lanthanide. Below pH 3, protonation of the phenol results in a flexible, open structure, leading to reversible demetallation of the lanthanide complex as the system comes under thermodynamic control. This study highlights the importance of a detailed understanding of both the speciation and pH responsive behavior of highly luminescent binuclear lanthanide complexes for their development as responsive probes. These results confirm the promise of phenolate derived binuclear complexes as highly luminescent responsive probes, modulated by changes in pH.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02305"},"PeriodicalIF":3.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937033","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}

引用次数: 0

The Important Role of the Polarization Effect in Cationic Hypervalent Chalcogen Bonds Catalysis. 极化效应在阳离子高价硫键催化中的重要作用。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-29 DOI: 10.1002/chem.202502391

Yanjiang Wang, Wen-Kai Chen, Yanli Zeng

{"title":"The Important Role of the Polarization Effect in Cationic Hypervalent Chalcogen Bonds Catalysis.","authors":"Yanjiang Wang, Wen-Kai Chen, Yanli Zeng","doi":"10.1002/chem.202502391","DOIUrl":"https://doi.org/10.1002/chem.202502391","url":null,"abstract":"Chalcogen bond (ChB) catalysts have recently garnered considerable attention in the field of organocatalysis owing to their advantages of nontoxicity, environmental sustainability, extensive applicability, affordability, and remarkable reactivity. In this work, the Se- and Te-based cationic hypervalent ChB catalysis on the bromolactonization reaction of N-Bromosuccinimide (NBS) with 4-pentenoic acid is investigated by high-level density functional theory (DFT) calculations. The ChB-catalyzed bromolactonization reaction has an intricate process involving bromine transfer, cyclization, and proton transfer. Moreover, the bromine transfer process is identified as the rate-determining step with the highest Gibbs free energy barrier. The increase in the size of the central atom in the ChB catalysts and the enhancement of electron-withdrawing capabilities with greater dipole moments of substitutions on the catalysts provide larger σ-holes with stronger polarization effects, resulting in stronger ChB interactions with the reactant, thus lowering the reaction barrier. From a kinetic perspective, different electron-withdrawing groups on the catalyst can be used to regulate the reaction rate, leading to better experimental outcomes. These findings demonstrate the important roles of polarization effects in cationic hypervalent chalcogen bonds catalysis and provide a theoretical foundation for the development of novel environmentally friendly and efficient hypervalent ChB catalysts.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02391"},"PeriodicalIF":3.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937116","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}

引用次数: 0

Acidity Controlled Formal Nucleophilic Substitution of Hydrofluoroolefin-based Iodonium Salt with O-nucleophiles: Synthetic Application and Mechanistic Study. 酸性控制的o -亲核试剂取代氢氟烯烃基碘盐的形式亲核：合成应用及机理研究。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-08-29 DOI: 10.1002/chem.202502254

János T Csenki, Dóra F Englert, Dániel Steinsits, Péter P Fehér, András Stirling, Zoltán Novák

{"title":"Acidity Controlled Formal Nucleophilic Substitution of Hydrofluoroolefin-based Iodonium Salt with O-nucleophiles: Synthetic Application and Mechanistic Study.","authors":"János T Csenki, Dóra F Englert, Dániel Steinsits, Péter P Fehér, András Stirling, Zoltán Novák","doi":"10.1002/chem.202502254","DOIUrl":"https://doi.org/10.1002/chem.202502254","url":null,"abstract":"The development and mechanistic investigation of a novel O-fluoroalkylation of phenol derivatives using a hypervalent fluoroalkyliodonium salt, derived from hydrofluoroolefin gas (HFO-1234yf) as bulk fluorous feedstock, is reported. Optimization of the reaction conditions enabled versatile and efficient synthetic applications, and the synthetic study revealed phenol acidity-dependent selectivity of the O-fluoroalkylation process. The mechanistic behavior of phenols was supported by both experimental studies and DFT calculations. As a result, we showed that more acidic phenols (pKa < 5) undergo direct O-alkylation, while reactions of the fluoroalkyliodonium salt involving less acidic phenol substrates proceed via a base-assisted chloride elimination and substitution pathway. Deuterium-labeling and halide competition experiments further validated the proposed mechanism. This practical and scalable method provides access to structurally diverse fluoroalkyl ethers and holds significant potential for applications in medicinal and materials chemistry.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02254"},"PeriodicalIF":3.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937111","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}

引用次数: 0