Chemistry - A European Journal最新文献

Front Cover: Design of Potent Mannose-6-Phosphate Derivatives as Ligands for CI-M6P/IGF2R Using Fluorescence Polarization Assay 封面：利用荧光偏振法设计强效甘露糖-6-磷酸衍生物作为CI-M6P/IGF2R的配体

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-23 DOI: 10.1002/chem.202584001

Lucie Mrázková, Klaudia Hladoníková, Barbora Toncarová, Michal Fischer, Jakub Zýka, Jaroslav Kozák, Michal Kráľ, Milan Kožíšek, Jiří Jiráček, Jakub Kaminský, Kamil Parkan, Lenka Žáková

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Cover Feature: Exploring the Impact of Phenanthroline-Based Glycoconjugated Ru(II) Polypyridyl Photosensitizers on Metastasis-Related Processes 封面专题：探讨基于菲罗啉的糖缀合Ru（II）多吡啶基光敏剂对转移相关过程的影响

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-23 DOI: 10.1002/chem.202584003

Elena de la Torre-Rubio, María-Selma Arias-Pérez, Lourdes Gude, Tomás Cuenca, Cristina García-Iriepa, Eva Royo

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Cover Feature: Tag-Assisted Liquid-Phase Oligonucleotide Synthesis: Toward a Convergent Approach 封面特征：标签辅助液相寡核苷酸合成：趋同方法

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-23 DOI: 10.1002/chem.202584002

Shinnosuke Akahane, Yuki Takahashi, Eimi Morikawa, Masae Sugai, Hideaki Umemoto, Takuya Onaka, Satoshi Ito, Naoto Taki, Yuya Yoshida, Yuto Toichi, Yoshikazu Kitano, Kazuhiro Chiba, Yohei Okada

引用次数: 0

Chalcogen-Guided Control of Azoarene Photoswitching: Tuning Excited-State Energies Through Electronic Property Modulation. 氮杂芳烃光电开关的硫导控制：通过电子特性调制调谐激发态能量。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202501571

Zoe Nonie Scheller, Jan Schulte, Christoph Wölper, Gebhard Haberhauer

{"title":"Chalcogen-Guided Control of Azoarene Photoswitching: Tuning Excited-State Energies Through Electronic Property Modulation.","authors":"Zoe Nonie Scheller, Jan Schulte, Christoph Wölper, Gebhard Haberhauer","doi":"10.1002/chem.202501571","DOIUrl":"https://doi.org/10.1002/chem.202501571","url":null,"abstract":"In recent years, chalcogen bonding has emerged as a promising alternative to classical supramolecular interactions such as hydrogen or halogen bonds. While its behavior in the electronic ground state has been extensively studied, its role in the excited state is gaining increasing attention. We recently demonstrated that the lack of photoswitchability of ortho-tellurated azobenzenes is due to an excitation-induced conversion of the classical chalcogen bond into a more pronounced, electron-rich three-electron σ bond. This transformation significantly strengthens the interaction between the chalcogen and the Lewis base center, effectively preventing isomerization. Based on these findings, we have now investigated the photoswitching behavior of ortho-tellurium-substituted azoarenes by modulation of the electronic properties of the aryl substituent and the oxidation state of the tellurium center. Our results show that electron-donating groups destabilize the excited-state geometry associated with the formation of a three-electron σ bond, thereby restoring photoisomerizability. Furthermore, oxidation to the Te(IV) species disrupts this bonding interaction, leading to significantly enhanced photoswitching properties. Together, these findings provide valuable design principles for the development of multiresponsive molecular switches based on chalcogen bonding and excited-state control.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01571"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681731","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 Polymer-Oriented Synthesis Of Triazinyl Functionalized Mesoporous Organic Polymer Encapsulating Uitrafine Metal Clusters for Alkynes Semi-Hydrogenation. 三嗪基功能化介孔有机聚合物包封氨基金属团簇用于炔半加氢的聚合物定向合成。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202501207

Rui Zhang, Shaohang Zheng, Luoqi Wang, Qingsong Li, Lichao Wang, Ling Zhang, Zhen-An Qiao

{"title":"A Polymer-Oriented Synthesis Of Triazinyl Functionalized Mesoporous Organic Polymer Encapsulating Uitrafine Metal Clusters for Alkynes Semi-Hydrogenation.","authors":"Rui Zhang, Shaohang Zheng, Luoqi Wang, Qingsong Li, Lichao Wang, Ling Zhang, Zhen-An Qiao","doi":"10.1002/chem.202501207","DOIUrl":"https://doi.org/10.1002/chem.202501207","url":null,"abstract":"Preparation of highly dispersed ultrafine metal clusters (MCs)- based catalysts with good stability and preeminent catalytic performance is a challenging problem for heterogeneous catalysis. Herein, we design and controllably synthesize a triazinyl functionalized mesoporous organic polymer (TRI-MOP) through a polymer-oriented synthesis strategy using polyethyleneimine (PEI) as pore-forming agent. The obtained TRI-MOP material possesses abundant worm-like mesopores, rich triazinyl groups, and high stability. Ultrafine Pd clusters with a small size (≈0.76 nm) are successfully anchored in the mesoporous channel of TRI-MOP by a simple impregnation-reduction approach. The as-prepared Pd@TRI-MOP catalyst exhibits excellent catalytic activity (96%) and selectivity (97%) in the semi-hydrogenation of phenylacetylene under very mild reaction conditions. The exceptional performance of Pd@TRI-MOP catalyst is attributed to the small size effect of Pd clusters, the electron coupling effect between the supports and the Pd and enriched meso-scaled pores. Therefore, this work provides a new platform for designing and preparing stable functional porous organic polymer materials to confine size-controlled MCs with superior catalytic performance for diversified potential catalysis applications.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01207"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681700","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

Polarization and Dipole Moment Effects on Sigma-Hole Potential in Tin(IV)-Porphyrins. 锡(IV)-卟啉中sigma -空穴电位的极化和偶极矩效应。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202502099

Rafia Siddiqui, Raphael F Ligorio, Hatem M Titi, Sushil Kumar Pandey, Anna Krawczuk, Ranjan Patra

{"title":"Polarization and Dipole Moment Effects on Sigma-Hole Potential in Tin(IV)-Porphyrins.","authors":"Rafia Siddiqui, Raphael F Ligorio, Hatem M Titi, Sushil Kumar Pandey, Anna Krawczuk, Ranjan Patra","doi":"10.1002/chem.202502099","DOIUrl":"https://doi.org/10.1002/chem.202502099","url":null,"abstract":"This study investigates how electron-withdrawing substitution, molecular polarization, and dipole moment influence the σ-hole potential in six-coordinate metalloporphyrins. To evaluate halogen bonding tendencies, we synthesized a series of five Sn(IV)-5,10,15,20-meso-tetrakis(4-iodophenyl)porphyrin complexes with various fluorinated phenolate axial ligands. Single-crystal X-ray diffraction analysis revealed distinct halogen-bonded supramolecular motifs, which vary depending on the degree of fluorination at the axial ligands. Our findings highlight the critical role of ligand-induced polarization and dipole moment variations in modulating the σ-hole characteristics of the equatorial iodine atoms. Computational modelling showed that increased fluorine substitution reduces both the atomic dipole moments of fluorine and the polarizability of the central tin ion. However, despite these changes, the axial fluorination has a negligible effect on the σ-hole potential at the iodine atoms. This limited influence is attributed to the orthogonal orientation between the porphyrin core and the peripheral phenyl rings, which suppresses resonance interactions. Overall, this work emphasizes the importance of understanding electronic effects at the molecular level, particularly in the design and formation of halogen-bonded supramolecular architectures.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02099"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681732","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

Base-Assisted Formation of Ferryl Species from TMC with Pendant N-Methylimidazole: Ligand and Base Effects on Fe^IV-Oxo Generation via O-O Bond Heterolysis. 悬垂n -甲基咪唑在TMC中碱辅助形成铁基：O-O键异解生成FeIV-Oxo的配体和碱效应

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202501652

Wei-Min Ching, Yi-Hsin Chen, Yu-Jie Tsai, Yu-Chieh Wang

{"title":"Base-Assisted Formation of Ferryl Species from TMC with Pendant N-Methylimidazole: Ligand and Base Effects on FeIV-Oxo Generation via O-O Bond Heterolysis.","authors":"Wei-Min Ching, Yi-Hsin Chen, Yu-Jie Tsai, Yu-Chieh Wang","doi":"10.1002/chem.202501652","DOIUrl":"https://doi.org/10.1002/chem.202501652","url":null,"abstract":"FeIV-oxo species can be generated using hydrogen peroxide via peroxidases, where the iron heme active site has a trans-imidazole. Here, we report the synthesis of FeII(TMC) complexes bearing pendant N-methylimidazole or pyridine donors using a modified reductive amination method. The structural characterization of complex 1 using ESI-Ms spectrometry, 1H-NMR spectroscopy, and X-ray crystallography revealed a distorted square-pyramidal geometry (τ = 0.45). The Fe-Nimidazole bond to N-methylimidazole was significantly shorter (2.066(6) Å) than that to pyridine (2.112 Å), indicating stronger electron donation from N-methylimidazole. For complex 2, the corresponding FeIV-oxo species was successfully generated using iodosylbenzene (PhIO)/hydrogen peroxide (H2O2) and characterized by UV-vis, 1H-NMR, FTIR spectroscopy, ESI-Ms spectrometry, and X-ray crystallography. The second-order rate constants (k2) of 2 with CHD and PPh3. are 0.14(0) and 0.50(1) M-1 s-1, respectively. In addition, the Kinetic analysis demonstrated a 1000-fold increase in the FeIV-oxo formation rate (kobs = 1.1(1)×10-1 s-1 for 2; 2.7(2) × 10-1 s-1 for 4) when 2,6-lutidine was replaced with triethylamine in the presence of H2O2. Eyring analysis revealed a heterolytic O-O bond cleavage mechanism for H2O2 (ΔH‡ = 19(1) kJ mol-1, ΔS‡ = -197(4) J/mol K for 2; ΔH‡ = 18(0) kJ/mol, ΔS‡ = -188(2) J mol-1K-1 for 4).","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01652"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681702","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

Breaking Bonds by Light: The Absorbance-Fragmentation Paradox. 光破坏化学键：吸收-破碎悖论。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202501839

Petra Dunkel, Christine Tran, Delphine Rigault, Bence Kontra, Eric Deprez, Patrick Tauc, Zoltán Mucsi, Hamid Dhimane, Peter I Dalko

引用次数: 0

Synthesis and Self-Assembly of a Discotic Oligo-Carboxylate Tetra-Porphyrin-Perylenebisimide Amphiphile. 盘状低聚羧酸四卟啉-苝酰二亚胺两亲化合物的合成与自组装。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202502093

Erik J Schulze, Mingjian Wu, Christina Hofmann, Erdmann Spiecker, Andreas Hirsch

{"title":"Synthesis and Self-Assembly of a Discotic Oligo-Carboxylate Tetra-Porphyrin-Perylenebisimide Amphiphile.","authors":"Erik J Schulze, Mingjian Wu, Christina Hofmann, Erdmann Spiecker, Andreas Hirsch","doi":"10.1002/chem.202502093","DOIUrl":"https://doi.org/10.1002/chem.202502093","url":null,"abstract":"We report the synthesis of an amphiphilic tetra-porphyrin perylenebisimide (PBI) conjugate via four-fold Suzuki cross-coupling at the PBI ortho-position. Oligo-carboxylate Newkome-type G1 dendrons attached at the porphyrin periphery serve as polar head groups. Theoretical modelling corroborated the assumed planar discotic geometry. The amphiphile is very soluble in mixtures of basic water and THF, where it displays strong aggregation at high water content. Insights into the self-assembly process were obtained by tracking the individualization through THF addition using UV/Vis absorption spectroscopy. Here, a PBI-centred aggregation motif becomes evident. Further evaluation of the morphology via STEM and TEM imaging reveals that the assembly is guided by hydrophobic interactions as well as interactions of the carboxylates. These ortho-linked tetra-porphyrin PBI architectures fill a gap within the known families of porphyrin-PBI conjugates. Furthermore, the amphiphile is a valuable addition to the library of amphiphilic porphyrin-PBI conjugates, representing a discotic counterpart to the known calamitic architectures.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02093"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681733","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

Tuning the Transparency and Exciton Transition of D-π-A-π-D Type Small Molecules. 调节D-π-A-π-D型小分子的透明度和激子跃迁。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-07-22 DOI: 10.1002/chem.202500657

Ecem Aydan Alkan, Houssam Metni, Patrick Reiser, Christian Kupfer, Juan S Rocha-Ortiz, Anastasia Barabash, Miroslaw Batentschuk, Jens A Hauch, Pascal Friederich, Christoph J Brabec

{"title":"Tuning the Transparency and Exciton Transition of D-π-A-π-D Type Small Molecules.","authors":"Ecem Aydan Alkan, Houssam Metni, Patrick Reiser, Christian Kupfer, Juan S Rocha-Ortiz, Anastasia Barabash, Miroslaw Batentschuk, Jens A Hauch, Pascal Friederich, Christoph J Brabec","doi":"10.1002/chem.202500657","DOIUrl":"https://doi.org/10.1002/chem.202500657","url":null,"abstract":"Organic small molecules possess significant potential for semitransparent optoelectronic applications due to their tunable optical properties and inherent transparency. However, tailoring these materials is challenging as their optoelectronic properties are sensitive to subtle structural changes, compounded by the existence of over a million potential structural designs. To address these complexities, we present a material discovery workflow that combines literature-based molecule preselection with TDDFT calculations, creating customized small molecule structures with adjustable transparency windows. We identified fifty-four small molecules with a D-π-A-π-D architecture, incorporating nine central (A) and six end (D) units connected by a thiophene π-bridge. Through TDDFT calculations, we determined the theoretical absorption spectra and energy levels of the identified molecules. Ultimately, we synthesized twenty-four molecules that exhibit promising transparency properties by selectively absorbing photons in the ultraviolet (UV) and near-infrared (NIR) regions, with a significant optical transmission band relevant to the visible spectrum, which we will refer to as \"optical window\". Characterization of the resultant small molecules revealed that six of them, in particular, exhibited selective absorption with the broadest \"optical window\". We believe that our study will provide valuable insights to establish an effective material discovery workflow for highly transparent conjugated organic small molecules.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e00657"},"PeriodicalIF":3.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681734","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