Chemistry - A European Journal最新文献

Enantioselective Route to Terminal 2,3-Epoxy Tosylates Enabled by Cooperative Organocatalytic Desymmetrization of 2-Substituted Glycerol Derivatives. 2-取代甘油衍生物协同有机催化脱对称催化的2,3-环氧甲酰酯对映选择途径

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-23 DOI: 10.1002/chem.202502523

Armando Astone, Sara Meninno, Alessandra Lattanzi

引用次数: 0

London Dispersion versus Intramolecular Hydrogen Bond in Bis-Pyridines: How Accurate Is DFT for Competing Noncovalent Interactions in the Condensed Phase? 双吡啶中的伦敦色散与分子内氢键：DFT对凝聚相中竞争非共价相互作用的准确性有多高？

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-23 DOI: 10.1002/chem.202502745

Adélaïde Savoy, Vladimir Gorbachev, Charlotte N Stindt, Peter Chen

{"title":"London Dispersion versus Intramolecular Hydrogen Bond in Bis-Pyridines: How Accurate Is DFT for Competing Noncovalent Interactions in the Condensed Phase?","authors":"Adélaïde Savoy, Vladimir Gorbachev, Charlotte N Stindt, Peter Chen","doi":"10.1002/chem.202502745","DOIUrl":"https://doi.org/10.1002/chem.202502745","url":null,"abstract":"We report a systematic investigation of noncovalent interactions-particularly an intramolecular hydrogen bond and London Dispersion forces-in singly protonated bis-pyridines, studied across solution and crystalline states. Building on our previous gas-phase study, we combine variable-temperature 1H NMR spectroscopy, single-crystal X-ray diffraction, and density functional theory (DFT) calculations. The measured 1H NMR chemical shifts of the acidic proton serve as a solution-phase structural readout, which we correlate with an independent crystallographic metric. By systematically varying the linker (-CH2-, -O-, and -CH2CH2-) and the pendant substituents (H, methyl, tert-butyl), we examine how increasingly bulky \"dispersion energy donors\" affect both the intramolecular hydrogen bond and the accessible conformational states. In reference systems, where a single noncovalent interaction governs the geometry, even relatively simple computational models correctly reproduce the experimentally observed structures. However, for molecules featuring two competing noncovalent interactions, the tested, dispersion-corrected, DFT often fails to predict the relative energies of accessible conformers accurately, highlighting current limitations in predictive accuracy. We briefly discuss broader implications of currently achievable predictive accuracy for homogeneous catalysis.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02745"},"PeriodicalIF":3.7,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342321","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

Trigonal Bipyramidal Clusters [Tl₅]^7-: Synthesis and Characterization of the Zintl Phase K_7-xA_xTl₅ (A = Rb, Cs; 0 < x ≤ 2.35). 三角双锥体簇[Tl5]7-: Zintl相K7-xAxTl5的合成与表征（A = Rb, Cs; 0 < x≤2.35）。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-23 DOI: 10.1002/chem.202502837

Vanessa F Schwinghammer, Tomáš Kovářík, Ilya G Shenderovich, Ján Minár, Stefanie Gärtner

{"title":"Trigonal Bipyramidal Clusters [Tl5]7-: Synthesis and Characterization of the Zintl Phase K7-xAxTl5 (A = Rb, Cs; 0 < x ≤ 2.35).","authors":"Vanessa F Schwinghammer, Tomáš Kovářík, Ilya G Shenderovich, Ján Minár, Stefanie Gärtner","doi":"10.1002/chem.202502837","DOIUrl":"https://doi.org/10.1002/chem.202502837","url":null,"abstract":"In alkali metal thallides, a huge variety of thallium clusters can be realized, which are surrounded only by alkali metals. In most cases, different cluster types are present in the crystal structures at the same time. One example is the [Tl5]7- trigonal bipyramid, which has only been observed beside [Tl9]9-, [Tl4]8-, [Tl3]7-, [Tl]5-, or [Tl8Cd3]10-. In the new ternary alkali metal thallide phase K7-xAxTl5 (A = Rb, Cs; 0 < x ≤ 2.35), exclusively [Tl5]7- clusters are present, and the compound can be described as a salt-like Zintl-phase, where the electron count is balanced in terms of the anionic moiety and counter cations. This phase crystallizes in the orthorhombic noncentrosymmetric space group Ama2. Different temperature programs applied during synthesis suggested metastability, which was subsequently proven by DSC measurements. DFT calculations reveal a minimum in the DOS at EF and support the salt-like description. Dissolution experiments in the style of well-known group 14 and group 15 solution chemistry in liquid ammonia were performed and showed oxidation of the alkali metal thallide. Initial 205Tl NMR studies in liquid ammonia allow for the detection of the first signal of a dissolved thallium species emerging from a thallide Zintl phase.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02837"},"PeriodicalIF":3.7,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342343","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

Cover Feature: A Structurally Unique {Fe(NO)2}10-{Fe(NO)2}9 Dinuclear Dinitrosyl Iron Complex Bridged by a μ-ƞ2-FBF3− Ligand and Stabilized by N-Heterocyclic Carbenes 覆盖特征：一种结构独特的{Fe(NO)2}10-{Fe(NO)2}9双核二硝基铁配合物，由μ-ƞ2-FBF3−配体桥接，n -杂环碳烯稳定

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-23 DOI: 10.1002/chem.70299

Yung-Chuan Chuang, Ching-Wen Lin, Yi-Hung Wu, Yu-Hsien Chang, Chung-Hung Hsieh

引用次数: 0

Front Cover: Deep Learning for Hyperpolarized NMR of Intrinsically Disordered Proteins Without Resolution Loss: Access to Short-Lived Intermediates 封面：无分辨率损失的内在无序蛋白质的超极化核磁共振深度学习：获取短寿命中间体

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-23 DOI: 10.1002/chem.70298

Ertan Turhan, Christopher Pötzl, Dörte Brandis, Federico Faglia, Milan Zachrdla, Dennis Kurzbach

引用次数: 0

Room-Temperature Paramagnetic-to-Diamagnetic Switching Behavior in an Open-Shell Ionic Liquid with a Tetracyanoquinodimethane Radical Anion Salt. 含四氰喹诺二甲烷自由基阴离子盐的开壳离子液体的室温顺磁-反磁开关行为。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202501449

Ruifeng Shu, Takeshi Naota, Masatoshi Kozaki, Daisuke Shiomi, Shuichi Suzuki

{"title":"Room-Temperature Paramagnetic-to-Diamagnetic Switching Behavior in an Open-Shell Ionic Liquid with a Tetracyanoquinodimethane Radical Anion Salt.","authors":"Ruifeng Shu, Takeshi Naota, Masatoshi Kozaki, Daisuke Shiomi, Shuichi Suzuki","doi":"10.1002/chem.202501449","DOIUrl":"https://doi.org/10.1002/chem.202501449","url":null,"abstract":"An ionic liquid consisting of a 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion and a tetra-n-octylphosphonium ion, 1+•TCNQ•-, undergoes a transformation near room temperature from paramagnetic liquid to diamagnetic solid accompanied by significant changes in photophysical properties. A blue solid of 1+•TCNQ•- melts upon heating above 328 K, yielding a green liquid. The green liquid exhibits a magnetic susceptibility of 5 × 10-4 emu mol- 1. Upon cooling, the liquid retains its paramagnetic properties until the temperature reaches approximately 300 K. Upon further cooling below 300 K, the paramagnetic liquid reverts to the initial blue solid. The solid form of 1+•TCNQ•- exhibits near-zero magnetic susceptibility. The thermal hysteresis loop with magnetic bistability is observed without decomposition over the temperature range from 300 to 328 K. Crystal structure analysis, electron spin resonance (ESR), and electronic spectra indicate that the drastic changes in magnetic properties are attributable to the reversible π-dimerization of TCNQ• - species during the solid-liquid/liquid-solid phase transitions. Additionally, the association/dissociation behaviors of the TCNQ• - dimers also induce significant changes in photophysical properties, especially in the short-wave infrared region (1000-2500 nm), suggesting the potential application of 1+•TCNQ•- as a bifunctional material.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01449"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342316","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

Substitution of CH₃ by CH₂F in 2-Methylerythritol Cyclodiphosphate Triggers Potent Inhibition of IspG with Concomitant Fluoride Ion Expulsion. 2-甲基赤藓糖醇环二磷酸中CH3被CH2F取代触发IspG的有效抑制并伴随氟离子排出。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202502471

Clea Witjaksono, Vivien Herrscher, Hannah Jobelius, Nathan Noël, Fabien Massicot, Jean-Luc Vasse, Jean-Bernard Behr, Myriam Seemann

{"title":"Substitution of CH3 by CH2F in 2-Methylerythritol Cyclodiphosphate Triggers Potent Inhibition of IspG with Concomitant Fluoride Ion Expulsion.","authors":"Clea Witjaksono, Vivien Herrscher, Hannah Jobelius, Nathan Noël, Fabien Massicot, Jean-Luc Vasse, Jean-Bernard Behr, Myriam Seemann","doi":"10.1002/chem.202502471","DOIUrl":"https://doi.org/10.1002/chem.202502471","url":null,"abstract":"IspG (also known as GcpE) is a key [4Fe-4S] metalloenzyme that catalyzes the penultimate step of the methylerythritol phosphate (MEP) pathway, a well-established target for the development of new antimicrobials. This oxygen-sensitive enzyme mediates the reductive dehydroxylation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate (MEcPP) to (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate (HMBPP), requiring electron transfer proteins to deliver two electrons needed for catalysis. To probe the mechanism of IspG and access new mechanism-based inhibitors, we synthesized a substrate analogue, monofluoromethyl-d-erythritol cyclodiphosphate, in which the natural methyl group of MEcPP is replaced by a CH2F group. This analogue proved to be a potent inhibitor of IspG. This study also demonstrates that electron capture is a prerequisite for inhibition and that the inhibitor leads to fluoride release in the IspG-catalyzed reaction. Together, these results provide further support for the involvement of a carbanionic intermediate in the IspG mechanism.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02471"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342296","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

Asymmetric Ligand Field Effects in Electron-Rich Heterometallic Extended Metal Atom Chain Compounds. 富电子杂金属延伸金属原子链化合物中的不对称配体场效应。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202502090

Rebecca K Walde, Trey C Pankratz, Amelia M Wheaton, Milton Acosta, John F Berry

{"title":"Asymmetric Ligand Field Effects in Electron-Rich Heterometallic Extended Metal Atom Chain Compounds.","authors":"Rebecca K Walde, Trey C Pankratz, Amelia M Wheaton, Milton Acosta, John F Berry","doi":"10.1002/chem.202502090","DOIUrl":"https://doi.org/10.1002/chem.202502090","url":null,"abstract":"In heterometallic systems, electron donation from the ligands may influence the metal atoms in either a symmetric or asymmetric way, with the expected case being that the more electronegative metal is favored. Here, we describe a systematic study of heterometallic compounds where this expectation is not observed. In this study, we use a modification of the symmetric 2,2'-dipyridylamine (dpa) ligand with electron donating ethyl groups, the 4,4'-diethyl-2,2'-dipyridylamine ligand (dedpa), to prepare heterometallic extended metal atom chain (HEMAC) complexes with formula Mo2M'(dedpa)4Cl2 (M' = Cr, Mn, Fe, Co, Ni). The effects of the electron donating substituents were studied through techniques including crystallography, magnetometry, cyclic voltammetry, EPR, Mössbauer, electronic absorption spectroscopy, and DFT calculations. We find that the new HEMACs are indeed more electron rich, easier to oxidize, and, most interestingly, the impact of the ethyl substituents is not applied equally to all the metals in the chain. The ligand field is stronger at the Mo2 site, but is surprisingly weaker at the M' center when compared to Mo2M'(dpa)4Cl2 complexes. We also find that changing the ligand field allows for previously unassigned electronic transitions to become visible, including excitations tentatively assigned to a triplet δ-δ* state within the Mo2 unit.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02090"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342283","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

Photo-enabled α-C(sp³)-H Functionalization of Sulfides. 硫化物的光使能α-C(sp3)-H功能化。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502638

Peng Cheng, Jie Ding, Zhenda Tan

引用次数: 0

NIR-II Organic Phototheranostics: Matching Rotatable Donors and Shielding Acceptors for Enhanced Imaging and Phototherapy by Stabilized Triplet Excitons and Optimized Radiative Decay. NIR-II有机光疗：通过稳定的三重态激子和优化的辐射衰变，为增强成像和光疗匹配可旋转供体和屏蔽受体。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502527

Jianye Gong, Yue Zhang, Jianguo Wang, Guoyu Jiang

{"title":"NIR-II Organic Phototheranostics: Matching Rotatable Donors and Shielding Acceptors for Enhanced Imaging and Phototherapy by Stabilized Triplet Excitons and Optimized Radiative Decay.","authors":"Jianye Gong, Yue Zhang, Jianguo Wang, Guoyu Jiang","doi":"10.1002/chem.202502527","DOIUrl":"https://doi.org/10.1002/chem.202502527","url":null,"abstract":"Second near-infrared (NIR-II) organic phototheranostic agents (OPTAs) have received significant interests in cancer treatment by enabling precise positioning of deep-seated lesions and highly efficient ablation of tumors. However, competition between radiative and nonradiative pathways of the excitons sets great obstacles for obtaining robust OPTAs. Herein, we propose to fabricate high-performance NIR-II OPTAs through molecular engineering of acceptor shielding units as well as manipulating molecular conformations by donor rotation. Accordingly, two series of OPTAs (BPN series: 4,4'-(ethene-1,1-diyl)bis(N,N-dimethylaniline) as rotatable donor and butadiene as π-bridge, BPTQ series: julolidine as donor and 2-vinylthiophene as π-bridge) with different acceptor shielding units were designed. Photophysical data and theoretical calculations verified the introduction of rotatable donors can help to realize highly twisted molecular conformations, resulting in enhanced NIR-II emission and photothermal conversion efficiency (PCE). Moreover, the adoption of acceptor shielding units is advantageous for stabilizing triplet excitons for radical reactive oxygen species (ROS) generation. As a result, a balance was achieved for BPN-P nanoparticles (NPs) in the BPN series, which exhibited high NIR-II emission, good radical ROS generation and highest PCE of 63%. BPN-P NPs achieved both high-resolution NIR-II angiography and imaging-guided synergistic photodynamic/photothermal cancer treatment in live mice model, showcasing the effectiveness of the strategy.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02527"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342260","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