Angewandte Chemie International Edition最新文献_第6页

Single-Step Synthesis of a Heterometallic [Cu2PdL4]2+ Hybrid Metal–Organic Coordination Cage 一步合成杂金属 [Cu2PdL4]2+ 混合金属有机配位笼

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-01 DOI: 10.1002/anie.202506064

David R. Turner, Shannon Thoonen, Samuel E. Walker, David L. Marshall, Therese M. Fulloon, Samuel Brandon, Alasdair I. McKay, Martin J. Paterson, Kathleen M. Mullen, James D. Crowley, Kellie L. Tuck

{"title":"Single-Step Synthesis of a Heterometallic [Cu2PdL4]2+ Hybrid Metal–Organic Coordination Cage","authors":"David R. Turner, Shannon Thoonen, Samuel E. Walker, David L. Marshall, Therese M. Fulloon, Samuel Brandon, Alasdair I. McKay, Martin J. Paterson, Kathleen M. Mullen, James D. Crowley, Kellie L. Tuck","doi":"10.1002/anie.202506064","DOIUrl":"https://doi.org/10.1002/anie.202506064","url":null,"abstract":"Traditional methods of assembling low-symmetry heterometallic cage architectures are limited to stepwise construction and combinations of inert and labile metal ions, affording complex, anisotropic cage structures by sacrificing synthetic ease. Herein, a heterometallic [Cu2PdL4]2+ lantern-type cage has been assembled in a single self-assembly step through the use of a heteroditopic ligand with two different metal-binding groups. The resultant cage complex is a fusion of two common lantern-type cage motifs – carboxylate-based metal–organic Cu4L4 cages and pyridyl-based Pd2L4 coordination cages. Evidence for heterometallic cage formation in solution was provided by 1H and diffusion-ordered NMR spectroscopy and electrospray ionisation mass spectrometry (ESI-MS) data, while circular dichroism (CD) spectra confirmed the helical nature of the assembly. The heterometallic cage was then exploited in binding heterotopic guests. It is envisioned that the simple design strategy presented herein will ease the assembly of other structurally complex, low-symmetry cage architectures.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745566","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}

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Aminomethyl Phosphonic Acid as Highly Effective Multifunctional Additive for Modification of Electron Transport Layer and Perovskite in Photovoltaic Solar Cells

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-01 DOI: 10.1002/anie.202424479

Yujie Gao, Wenyu Gong, Zeqi Zhang, Jianing Guo, Jingyuan Ma, Xuan Li, Yanli Zeng, Mingxing Wu

{"title":"Aminomethyl Phosphonic Acid as Highly Effective Multifunctional Additive for Modification of Electron Transport Layer and Perovskite in Photovoltaic Solar Cells","authors":"Yujie Gao, Wenyu Gong, Zeqi Zhang, Jianing Guo, Jingyuan Ma, Xuan Li, Yanli Zeng, Mingxing Wu","doi":"10.1002/anie.202424479","DOIUrl":"https://doi.org/10.1002/anie.202424479","url":null,"abstract":"The passivation of detrimental perovskite-based defects is critically acknowledged for fabricating highly effective perovskite solar cells (PSCs). The presence of a high-quality electron transport layer (ETL) is also considered a pivotal factor for effective charge extraction and transport dynamics. Herein, a simple small organic molecule, aminomethyl phosphonic acid (AMPA), is introduced as a multifunctional additive in the SnO2 ETL. The defects in the SnO2 ETL are effectively suppressed by passivating the oxygen vacancies upon the SnO2 surface. Simultaneously, the carrier mobility and crystallinity of SnO2 are enhanced, and the upward-regulated conduction band minimum (CBM) is beneficial for constructing a favourable energy level alignment with the perovskite layer. Notably, the introduced residuals on the SnO2 surface can function as crystalline seeds for growth of large perovskite grains, which can passivate the defects in the perovskite bulk phase, boundaries, as well as the SnO2/perovskite interface. Consequently, the power conversion efficiency (PCE) value of the AMPA-modified PSCs is enhanced from 19.91% to 24.22%. Most importantly, the unencapsulated PSCs with AMPA maintained 94.9% of the initial PCE during 720 h of storage at a relative humidity of 10%, attributed to the improved hydrophobicity of both the SnO2 and perovskite layers after AMPA modification.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745565","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

Introducing the aziridination of fluorinated olefins by metal-catalyzed nitrene transfer

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-01 DOI: 10.1002/anie.202419188

Jorge Pérez-Ruíz, Antonio Rosales-Martínez, Pedro J. Pérez, M. Mar Díaz-Requejo

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Self‐Optimized Reconstruction of Metal‐Organic Frameworks Introduces Cation Vacancies for Selective Electrosynthesis of Hydrogen Peroxide

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-01 DOI: 10.1002/anie.202501930

Chao Miao, Shaohan Xu, Ziwen An, Xun Pan, Yanbo Li, Nan Hu, Lina Li, Yongxin Zhou, Guohua Zhao

{"title":"Self‐Optimized Reconstruction of Metal‐Organic Frameworks Introduces Cation Vacancies for Selective Electrosynthesis of Hydrogen Peroxide","authors":"Chao Miao, Shaohan Xu, Ziwen An, Xun Pan, Yanbo Li, Nan Hu, Lina Li, Yongxin Zhou, Guohua Zhao","doi":"10.1002/anie.202501930","DOIUrl":"https://doi.org/10.1002/anie.202501930","url":null,"abstract":"The electrocatalytic synthesis of hydrogen peroxide (H2O2) through the two‐electron oxygen reduction pathway represents a green production process that has gained increasing importance. Nevertheless, there is a dearth of efficacious catalysts to attain high activity under industrial current density. In this study, we present a strategy for cation vacancy generation through metal‐organic frameworks self‐optimized reconfiguration for the efficient electrosynthesis of H2O2 under industrial current densities in solid‐electrolyte cell. The ZIF‐ZC91@Co(OH)2‐VCo electrocatalyst exhibits significant H2O2 selectivity of 97.8%, and the H2O2 productivity is up to 24.53 mol gcatalyst−1 h−1 with a direct and continuous output of ~3.36 wt% H2O2 aqueous solutions under industrial current density (400 mA cm−2). Impressively, the ZIF‐ZC91@Co(OH)2‐VCo possesses superb long‐term durability for over 220 h and can output H2O2 aqueous solution with a concentration of ~8.03 wt% in the pilot experiment. Theoretical calculations confirm that the introduction of modest cation vacancies optimizes the adsorption strength of *OOH intermediate and reduces both thermodynamic and kinetic barriers, thus balancing the selectivity of the two‐electron oxygen reduction. This work provides valuable insights into the rapid, eco‐friendly synthesis of H2O2 and the rational design of highly active catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745096","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}

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Insertion of Nitriles into a Gold(III)/Carbene Bond: A Direct and Powerful Entry to Imino-Substituted Carbenes

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504162

Rui Wei, Nina Albouy, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou

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Harnessing molecular recognition for small molecule-mediated, reversible photochemical control over mRNA translation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202503078

Shaifaly Parmar, Logan Tenney, Xiao Liang, John T. Routzahn, Christopher D. Sibley, John Schneekloth

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Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second-Harmonic Generation and Full-Wavelength Phase Matching

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504673

Min-Quan Lin, Chun-Li Hu, Meng-Fan Duan, Bing-Xuan Li, Jiang-Gao Mao, Bing-Ping Yang

{"title":"Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second-Harmonic Generation and Full-Wavelength Phase Matching","authors":"Min-Quan Lin, Chun-Li Hu, Meng-Fan Duan, Bing-Xuan Li, Jiang-Gao Mao, Bing-Ping Yang","doi":"10.1002/anie.202504673","DOIUrl":"https://doi.org/10.1002/anie.202504673","url":null,"abstract":"The development of nonlinear optical materials with large nonlinear optical susceptibilities, wide transmission ranges, and comprehensive full-wavelength phase matching capabilities remains a significant challenge. In this study, we synthesized a novel potassium tetraiodatoiodate(III) iodate(V) via an in situ reduction and complexation reaction. The resulting compound, K2[IIII(IVO3)4]IVO3, exhibits exceptional second harmonic generation responses (21.6KH2PO4 at 1064 nm, 1.0KTiOPO4 at 2050 nm), a wide transparency range from the visible to the mid-infrared wavelengths (0.37–6.05 μm and 7.03–13.40 μm), and a high birefringence (0.358 at 543 nm) to achieve full-wavelength phase matching. These properties are primarily ascribed to the synergistic substantial hyperpolarizability and polarizability anisotropy exhibited by the [IIII(IVO3)4]− complex ions, which comprise square-planar coordinated trivalent iodine and optimally arranged iodate ligands. This study demonstrates the pivotal role of nonmetallic cation centered coordination entities in influencing linear and nonlinear optical properties, a discovery that has significant implications for the development of innovative inorganic functional materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"76 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737286","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}

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Concise Total Syntheses of Leuconoxine-Type Alkaloids Enabled by Palladium/Norbornene-Catalyzed Pyrrole Difunctionalization

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202502736

Xin Liu, Yun Zhou, Yu Meng, Qi Zhu, Renhe Li, Guangbin Dong

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Oxygen Atom Migration Dominates Anomalous Reversible Oxidation of Ru Nanosheets

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202502927

Xiong Xiao, Yongli Shen, Wei Xi, Lin Gu, Xiaogang Li, Baojuan Xi, Shenglin Xiong, Changhua An

{"title":"Oxygen Atom Migration Dominates Anomalous Reversible Oxidation of Ru Nanosheets","authors":"Xiong Xiao, Yongli Shen, Wei Xi, Lin Gu, Xiaogang Li, Baojuan Xi, Shenglin Xiong, Changhua An","doi":"10.1002/anie.202502927","DOIUrl":"https://doi.org/10.1002/anie.202502927","url":null,"abstract":"Oxidation is a ubiquitous reaction in nature. For most metals (especially metal nanoparticles), they will be completely oxidized under suitable conditions, except ruthenium (Ru). In this work, in‐situ transmission electron microscopy (in‐situ TEM) and ex‐situ spectroscopy were employed to investigate the oxidation process of Ru nanosheets. Ex‐situ spectroscopic analysis demonstrates the incomplete oxidation of Ru nanosheets to RuO₂, while the in‐situ TEM observations uncover an anomalous reverse phase transformation from the oxidized to metallic phase during oxidation. Combined with theoretical calculations, the oxygen atom migration dominates the reversible oxidation process, strikingly distinct from the unidirectional oxidation pathways in conventional metallic systems. The as‐generated abundant Ru‐RuO2 heterointerfaces formed through reversible oxidation provide a wealth of active sites for electrochemical alkaline hydrogen evolution reaction (HER). Herein, the study not only lays a foundation for the understanding complex dynamic oxidation processes, but also offers new insights into for the design of nanocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736720","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

Annulated Radical Cations with a C4E2‐Core (E = P, As, Sb): Stable Pnictogen Analogs of Elusive Aryl Radical Anions of Birch Reduction Reactions

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202505142

Henric Steffenfauseweh, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler Stammler, Demi Snabilié, Bas de de Bruin, Rajendra Ghadwal

{"title":"Annulated Radical Cations with a C4E2‐Core (E = P, As, Sb): Stable Pnictogen Analogs of Elusive Aryl Radical Anions of Birch Reduction Reactions","authors":"Henric Steffenfauseweh, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler Stammler, Demi Snabilié, Bas de de Bruin, Rajendra Ghadwal","doi":"10.1002/anie.202505142","DOIUrl":"https://doi.org/10.1002/anie.202505142","url":null,"abstract":"The benzene radical anion (C6H6)●–, possessing a 7π‐electron count, is a crucial intermediate in the Birch reduction and has been extensively studied both experimentally and theoretically. Herein, we report the tricyclic pnictogen radical cations [(ADC)E]2[B], [2‐E][B] (ADC = PhC{N(Dipp)C}2; Dipp = 2,6‐iPr2C6H3; E = P, As, Sb; [B] = [B1] = B(C6F5)4 or [B2] = {3,5‐(CF3)2C6H3}) featuring a central 7π‐electron planar C4E2 ring embedded between two 1,3‐imidazole‐based anionic dicarbene (ADC) frameworks, as crystalline solids. [2‐E][B] are prepared by one‐electron (1e) oxidations of the corresponding base‐stabilized cyclic pnictinidene compounds [(ADC)E]2 (1‐E). Calculated spin densities (for E = P 76%, As 80%, Sb 88%) and EPR measurements suggest that [2‐E]●+ are pnictogen‐centered radicals and stabilized by the delocalization of the unpaired electron over the C4E2 ring. The EPR spectra of [2‐E][B] exhibit characteristic signals for S = ½ systems with clear hyperfine coupling constants for the two similar P, As or Sb nuclei. Further 1e‐oxidations of [2‐E][B] result in the dicationic 6π‐electron C4E2‐species [(ADC)E]2[B]2 [3‐E][B]2, which readily undergo comproportionations with 1‐E to afford [2‐E][B]. The radical reactivity of [2‐E][B2] is shown with 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO) and diphenyl diselenide (PhSeSePh) in yielding compounds [(ADC)2E{E(TEMPO)}][B2] (4‐E) (E = P, Sb) and [(ADC)2P{P(SePh)}][B2] (5‐P), respectively.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"96 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736742","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