Angewandte Chemie International Edition最新文献

Engineering Cavity and Aperture Binding Sites Within a Metal–Organic Cage for Up‐ and Down‐Regulation of Catalysis 金属-有机笼内的工程腔和孔径结合位点用于催化的上下调节

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202507981

Yan Xu, Gen Li, Shihang Liang, Gaël De Leener, Michel Luhmer, Roy Lavendomme, En‐Qing Gao, Dawei Zhang

{"title":"Engineering Cavity and Aperture Binding Sites Within a Metal–Organic Cage for Up‐ and Down‐Regulation of Catalysis","authors":"Yan Xu, Gen Li, Shihang Liang, Gaël De Leener, Michel Luhmer, Roy Lavendomme, En‐Qing Gao, Dawei Zhang","doi":"10.1002/anie.202507981","DOIUrl":"https://doi.org/10.1002/anie.202507981","url":null,"abstract":"Engineering molecular recognition events into catalytic systems to precisely control the up‐ or down‐regulation of catalysis in a biomimetic fashion is a challenging goal in supramolecular chemistry. In this work, we report on the construction of a new metal–organic cage, ZnII4L4 tetrahedron 1, using a protonated azacalix[3](2,6)pyridine‐based ligand as the capping faces. The cage features a large cavity and wide gaps between its faces, enabling the simultaneous binding of anionic guests centrally and peripherally. Encapsulation of α‐Mo8O264− within the T‐symmetric tetrahedron 1 leads to a C3‐symmetric inclusion complex Mo8O264−⊂1. The apertures of Mo8O264−⊂1 act as secondary binding sites for accommodating tetraarylborate guests or for providing access to the included Mo8O264− for catalyzing reactions. Catalytic experiments demonstrated that inclusion within 1 significantly enhances the catalytic activity of Mo8O264− for the oxidation of sulfides into sulfoxides. In contrast, peripheral binding of the bulky tetraarylborate anion to the inclusion complex Mo8O264−⊂1 effectively inhibits its catalytic activity by obstructing access to the catalytic active sites of Mo8O264−.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Stabilizing Cu3+ Active Center by Intramolecular Electron Transfer for Boosting Complete Glucose Electrooxidation 通过分子内电子转移稳定Cu3+活性中心促进葡萄糖完全电氧化

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202511103

Rui Zheng, Long Pang, Zhangquan Peng, Dongyang Qu, Yu Bao, Huiliang Sun, Zhonghui Sun, Shaojun Guo, Li Niu

{"title":"Stabilizing Cu3+ Active Center by Intramolecular Electron Transfer for Boosting Complete Glucose Electrooxidation","authors":"Rui Zheng, Long Pang, Zhangquan Peng, Dongyang Qu, Yu Bao, Huiliang Sun, Zhonghui Sun, Shaojun Guo, Li Niu","doi":"10.1002/anie.202511103","DOIUrl":"https://doi.org/10.1002/anie.202511103","url":null,"abstract":"The development of effective electrocatalysts for glucose (Glu) electro‐conversion is highly desirable for sensing applications; however, is greatly plagued by unstable catalytic active centers during the catalytic process, leading to severe inactivation of active sites and incomplete Glu electrooxidation. Herein, we report a class of single‐atom Pt‐doped Cu‐based metal‐organic frameworks (MOFs) with stable high‐valence Cu sites (CuO‐MOF‐Pt1), achieving a complete oxidation of Glu and a milliampere current response toward Glu. We demonstrate that the –CN of MOF and Pt serve as electron‐withdrawal sites to induce electron transfer of the Cu site, promoting the electrochemical generation of the stabilized Cu3+ active center. Using operando spectroscopy and computation, we uncover that a complete glucose electrooxidation reaction (GOR) can be achieved by successive C─C bond scission over CuO‐MOF‐Pt1, and a stable Cu3+ active center is responsible for its impressive GOR activity. Notably, CuO‐MOF‐Pt1 delivers comparable Glu sensing performance with a high sensitivity of 2.587 mA mM−1 cm−2, a low detection limit of 0.93 µM, and extraordinary durability. We further constructed a miniaturized CuO‐MOF‐Pt1‐based sensor, enabling accurate detection of Glu in saliva. This work opens an inspiring avenue to the precise design of stable metal activity centers through electronic structure regulation for boosting Glu electrooxidation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"138 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Single-Step Insertion of Organic Sulfur Into a Fe6C Carbide Carbonyl Cluster, Including the Natural Amino Acid L-Cysteine: Vibrational Circular Dichroism and Chirality Transfer. 含天然氨基酸l -半胱氨酸的Fe6C碳化物羰基簇中有机硫的一步插入：振动圆二色性和手性转移。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202513702

Francesca Forti,Andrea Pellegrini,Cristiana Cesari,Cristina Femoni,Maria Carmela Iapalucci,Michele Mancinelli,Stefano Zacchini

{"title":"Single-Step Insertion of Organic Sulfur Into a Fe6C Carbide Carbonyl Cluster, Including the Natural Amino Acid L-Cysteine: Vibrational Circular Dichroism and Chirality Transfer.","authors":"Francesca Forti,Andrea Pellegrini,Cristiana Cesari,Cristina Femoni,Maria Carmela Iapalucci,Michele Mancinelli,Stefano Zacchini","doi":"10.1002/anie.202513702","DOIUrl":"https://doi.org/10.1002/anie.202513702","url":null,"abstract":"We present a straightforward and versatile synthetic route to Fe6C carbide carbonyl clusters containing organosulfur ligands, including the chiral amino acid L- and D-cysteine. Reaction of the reduced cluster [NEt4]4[Fe6C(CO)15] (1) with thiols (RSH) or disulfides (RSSR) affords novel functionalized hexa-iron carbide clusters [NEt4]3[Fe6C(CO)14(SR)] (R = CH3, 2; C6H5, 3; p-C6H4CH3, 4; L-cysteine, L-5; D-cysteine, D-5). Compounds 2-5 have been characterized by Fourier transform infrared (FT-IR), 1H and 13C{1H} nuclear magnetic resonance (NMR) spectroscopy, and the molecular structures of 2-4 have been determined by single-crystal X-ray diffraction (SC-XRD). The chirality of the L-5 and D-5 enantiomers has been investigated by vibrational circular dichroism (VCD), and this represents the first VCD study of chiral metal carbonyl clusters. Combined analyses of VCD and calculated density functional theory (DFT) spectra clearly point out the occurrence of chirality transfer from the chiral organosulfur ligand to the CO ligands, as indicated by the presence of VCD bands in the νCO region of both L-5 and D-5. This unprecedented transfer of chirality among different ligands arises from close interactions between the CH2 and CH hydrogens of coordinated cysteine and the CO shell of the clusters.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"733 1","pages":"e202513702"},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Expanding the Synthetic Playbook with a Biochemical Twist: The 58th Bürgenstock Conference 用生化扭曲扩展合成剧本：第58届<s:1>根斯托克会议

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202515683

Manuel Nappi, Giulio Ragazzon

引用次数: 0

Semiconductor Cluster with High Reduction Potential and Efficient Charge Transfer Enables Visible‐Light‐Driven Activation of Inert Organic Substrates 具有高还原电位和高效电荷转移的半导体团簇实现了惰性有机衬底的可见光驱动活化

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202509764

Hao Ma, Cheng‐Kun Han, Jia‐Xing Liu, Yi‐Lei Xu, Chao‐Li Chen, Xu‐Hang Zhong, Li‐Yang Chen, Rui Zhou, Bingzhe Wang, Junhui Wang, Jingyi Zhu, Kaifeng Wu, Dong‐Sheng Li, Tao Wu, Shang‐Fu Yuan

{"title":"Semiconductor Cluster with High Reduction Potential and Efficient Charge Transfer Enables Visible‐Light‐Driven Activation of Inert Organic Substrates","authors":"Hao Ma, Cheng‐Kun Han, Jia‐Xing Liu, Yi‐Lei Xu, Chao‐Li Chen, Xu‐Hang Zhong, Li‐Yang Chen, Rui Zhou, Bingzhe Wang, Junhui Wang, Jingyi Zhu, Kaifeng Wu, Dong‐Sheng Li, Tao Wu, Shang‐Fu Yuan","doi":"10.1002/anie.202509764","DOIUrl":"https://doi.org/10.1002/anie.202509764","url":null,"abstract":"Photoredox catalysis is an essential component of modern organic synthesis. However, current photocatalysts face the challenge of simultaneously requiring strong redox potentials and efficient charge transfer to meet the thermodynamic and kinetic demands of photoinduced electron transfer processes. Herein, we present an excellent reactivity mode for photocatalysis based on semiconductor clusters, exploiting the ideal Marcus parabola to couple potential and kinetic requirements. Our system demonstrates an exceptionally high negative reduction potential (Ered) (−2.94 V versus SCE, on par with K0) and realizes efficient charge transfer—rapid charge separation (CS) and slow charge recombination (CR) kinetics. This duality endows the protocol with remarkable versatility by enabling the dearomatization of nonactivated arenes and reductive dehalogenation of challenging aryl/alkyl chlorides and aryl fluorides, as well as arylation and amination, with a high functional group tolerance under visible‐light irradiation. Furthermore, this platform offers easy recyclability, supports gram‐scale synthesis, and can be extended to the late‐stage functionalization and deuteration of drugs. This innovative catalytic platform provides a new approach for the photochemical activation of inert organic substrates and is foreseen to promote the development of radical reaction‐based pharmaceutical synthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"77 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Privileged Chiral Photocatalysts 特权手性光催化剂

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202513320

Emanuel Studer, Smita Mandal, Timo Stünkel, Ryan Gilmour

{"title":"Privileged Chiral Photocatalysts","authors":"Emanuel Studer, Smita Mandal, Timo Stünkel, Ryan Gilmour","doi":"10.1002/anie.202513320","DOIUrl":"https://doi.org/10.1002/anie.202513320","url":null,"abstract":"Privileged chiral catalysts have transformed asymmetric synthesis, conferring generality to processes that are routinely leveraged in the construction of societally important functional small molecules. Operating in the ground state, these catalysts are conspicuous in their ability to simultaneously regulate reactivity and translate chiral information, often with broad substrate tolerance: this technology continues to expedite chemical space exploration. In stark contrast to the specificity of many enzymatic transformations, this promiscuity affords remarkable latitude for creative endeavour in synthesis. Given the transformative impact that stereoselective photocatalysis has had over the last decade, identifying privileged chiral catalysts that permit reactivity and enantioselectivity to be regulated in excited‐state scenarios has emerged as an attractive but challenging frontier. Providing solutions to address this paradox will require the reactivity/selectivity divide to be reconciled through the validation of chiral scaffolds that effectively operate in non‐ground state environments. Inspired by the venerable treatment by Yoon and Jacobsen entitled “Privileged chiral catalysts” (Science 2003, 299, 1691–1693), this mini‐review is intended to survey the conception and evolution of privileged chiral photocatalyst scaffolds, and offer a perspective on emerging contenders.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Multisite Cooperative Regulation of Solvation and Interface via Dynamic Additive Engineering for Highly Reversible Zinc Batteries 基于动态添加剂工程的高可逆锌电池溶剂化和界面多位点协同调节

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202511685

Mengke Su, Haozhen Dou, Jinliang Yan, Sitong Liu, Mi Xu, Chuangwei Liu, Xin Wang, Zhongwei Chen

{"title":"Multisite Cooperative Regulation of Solvation and Interface via Dynamic Additive Engineering for Highly Reversible Zinc Batteries","authors":"Mengke Su, Haozhen Dou, Jinliang Yan, Sitong Liu, Mi Xu, Chuangwei Liu, Xin Wang, Zhongwei Chen","doi":"10.1002/anie.202511685","DOIUrl":"https://doi.org/10.1002/anie.202511685","url":null,"abstract":"Inexhaustible additives have been reported to enhance the reversibility of aqueous zinc‐ion batteries (AZIBs). However, the structure–performance relationship of additive molecules remains elusive, particularly regarding multisite coordination‐mediated synergistic regulation of solvation and interface. Herein, a dynamic configuration reconstruction mechanism that orchestrates the multisite regulation of solvation and interface is unveiled by utilizing a series of polyhydroxy additive prototypes, demonstrating that the increase of functional groups and chain flexibility in multifunctional‐group molecules (MGMs) contributes to boosting battery performance. MGM with folded configuration engages in multisite Zn2+ coordination in the solvation shell, effectively minimizing active H2O molecule to suppress parasitic reactions, while its configuration transition to straight‐chain architecture enables multisite parallel adsorption on Zn anode interface, thus accelerating desolvation kinetics and steering (002)‐facet‐dominated Zn deposition. Remarkably, Zn//Zn cells achieve long cycle life of 7000 h and subzero‐temperature operation, and Zn//PANI pouch cell maintains nearly 100% capacity retention after 500 cycles. This work opens a fascinating avenue for developing high‐performance batteries via dynamic additive engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Jimin Park Jimin公园

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202515276

Jimin Park

引用次数: 0

Metallaphosphirenes with σ‐Aromaticity: Capture of Phosphorus Atom by Metalla‐Aromatics 具有σ -芳香性的金属膦烯：金属芳烃对磷原子的捕获

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202512214

Xin Yang, Xiaoyan Zhang, Yapeng Cai, Haiping Xia, Hong Zhang

引用次数: 0

Long Range Coherent Energy Transfer in Artificial Multichromophoric Antenna Systems—A Case of Breaking Kasha's Rule 人工多色天线系统中的远程相干能量传输——一个打破卡沙规则的例子

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-08-01 DOI: 10.1002/anie.202513001

Maryam Nazari Haghighi Pashaki, Caroline D. Bösch, Florian Garo, Ambre Blanc, Marco Marazzi, Ariana Rondi, Michela Gazzetto, Maryam Akbarimoosavi, jean‐christophe Tremblay, Simon Matthias Langenegger, Antonio Monari, Robert Häner, Thomas Feurer, Andrea Cannizzo

引用次数: 0