Angewandte Chemie International Edition最新文献_第2页

Hydrogen Isotope Exchange in Pyridine Catalyzed by an Iron(II) Imido Complex: Counterion-Directed Regioselectivity 铁（II）亚胺配合物催化吡啶中氢同位素交换：反离子定向区域选择性

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-28 DOI: 10.1002/anie.4646822

Bin Feng, Guorong Li, Yafei Gao, Nobuyuki Yamamoto, Maren Pink, Qian Peng, Jeremy M. Smith

{"title":"Hydrogen Isotope Exchange in Pyridine Catalyzed by an Iron(II) Imido Complex: Counterion-Directed Regioselectivity","authors":"Bin Feng, Guorong Li, Yafei Gao, Nobuyuki Yamamoto, Maren Pink, Qian Peng, Jeremy M. Smith","doi":"10.1002/anie.4646822","DOIUrl":"https://doi.org/10.1002/anie.4646822","url":null,"abstract":"High-spin (S = 2) iron(II) imido complexes [Ph2B(tBuIm)2Fe═NDipp]M (M = Li+, K+, K(18-c-6)+) are catalysts for the hydrogen isotope exchange (HIE) reaction with pyridine as the substrate. As dictated by the counter-cation, these complexes catalyze site-selective α-, α,β,γ-, and β,γ-deuteration of pyridine. Experimental and computational mechanistic investigations reveal the critical role of the counter-cation in catalysis, which activates the substrate, facilitates deuteration, and dictates HIE regioselectivity. The stoichiometric reaction of pyridine with [Ph2B(tBuIm)2Fe═NDipp]Li affords the catalytically active bis(2-pyridyl) complex [Ph2B(tBuIm)2Fe(2-Py)2Li(THF)2]. By maintaining coordination to the substrate during the catalytic cycle, Li+ preorganizes pyridine for regioselective α-deuteration by this catalyst. On the other hand, [Ph2B(tBuIm)2Fe═NDipp]K reacts with pyridine to afford the 2-pyridyl amido complex [Ph2B(tBuIm)2Fe(2-Py)NHDipp]−, which has been structurally characterized with [K(18-c-6)(THF)2]+ and [K(dibenzo-18-c-6)(THF)2]+ counterions. As dictated by the size of the counter-cation, [Ph2B(tBuIm)2Fe═NDipp]− catalyzes regioselective α,β,γ- and β,γ-deuteration of pyridine. Here, the counter-cation stabilizes the appropriate pyridyl regioisomer for the selectivity-determining deuteration step.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e4646822"},"PeriodicalIF":16.6,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755241","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

Reactant‑Transporting Metal-Support Interaction for Lattice Carbonate‑to‑Methane Catalysis 晶格碳酸盐-甲烷催化反应的反应物运输金属-载体相互作用

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-28 DOI: 10.1002/anie.7839925

Guangxing Yang, Hanke Li, Yiming Niu, Chengxiong Dang, Yonghai Cao, Hongjuan Wang, Hao-Fan Wang, Bingsen Zhang, Feng Peng, Hao Yu

{"title":"Reactant‑Transporting Metal-Support Interaction for Lattice Carbonate‑to‑Methane Catalysis","authors":"Guangxing Yang, Hanke Li, Yiming Niu, Chengxiong Dang, Yonghai Cao, Hongjuan Wang, Hao-Fan Wang, Bingsen Zhang, Feng Peng, Hao Yu","doi":"10.1002/anie.7839925","DOIUrl":"https://doi.org/10.1002/anie.7839925","url":null,"abstract":"As a core concept of heterogeneous catalysis, metal-support interactions are pivotal controlling activity, selectivity, and stability via electronic and geometric effects. Here, we report a reactant‑transporting form of metal support interaction (MSI), named as strong metal-reactive support interaction (SMRSI) where Pt/H2 directly hydrogenates lattice carbonate in calcite to CH4 with ≤ 415 °C onset and ∼98% selectivity (390–510°C). Because lattice carbon in carbonate minerals constitutes Earth's largest carbon reservoir, enabling low‑temperature lattice–carbonate conversion offers a catalytic lever to accelerate the slow carbon cycle (ACC) complementary to fast carbon cycle (FCC)‑based CO2 management. Operando techniques show a permeable amorphous interphase that dynamically encapsulates Pt, transports CO32− to active sites, and crystallizes into Ca(OH)2, thereby sustaining a mobile triple‑phase boundary, where carbonate‑derived *CO intermediate was hydrogenated to CH4. It is resolved that a low‑temperature interfacial CO2 release is diagnostic of boundary decomposition. Kinetics separate a CO32−‑diffusion‑limited solid‑state path at low temperatures from a high‑temperature route akin to gaseous‑CO2 hydrogenation. The hydrogenated solid is re-carbonated by CO2, regenerating CaCO3 and retaining selectivity over cycles. Conceptually, the SMRSI extends MSI from electronic/geometric tuning to reactant transport, illustrating how moving solid-solid@gas interfaces mediate transformations of solid reactants.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"70 1","pages":"e7839925"},"PeriodicalIF":16.6,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755236","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

Electrochemical Divergent Synthesis of Azetidines via Strain Release of 1‑Azabicyclo[1.1.0]butanes. 1 -氮杂环[1.1.0]丁烷释放的电化学发散合成氮杂啶。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.5707597

Neelam Duhan,Shiv Dutt,Sumit K Rastogi,Prabal Banerjee

{"title":"Electrochemical Divergent Synthesis of Azetidines via Strain Release of 1‑Azabicyclo[1.1.0]butanes.","authors":"Neelam Duhan,Shiv Dutt,Sumit K Rastogi,Prabal Banerjee","doi":"10.1002/anie.5707597","DOIUrl":"https://doi.org/10.1002/anie.5707597","url":null,"abstract":"Due to the favorable pharmaceutical properties of the azetidine ring, it can serve as a bioisostere to replace saturated heterocycles such as piperazines, piperidines, and pyrrolidines in drug discovery. The diverse methods for azetidine synthesis are still limited and challenging. Herein, we design a new class of 1-azabicyclo[1.1.0]butanes (ABBs) and report the first electrochemical protocol for the synthesis of chemo-selective trifluoromethanesulfonylated and trifluoromethylated azetidine derivatives via direct anodic oxidation. The key features of this strategy involve: (i) electrochemical anodic oxidation of ABB to form a N-centered radical cation, (ii) a rare [2,3]-sigmatropic shift of sulfone, (iii) selective oxidation of Langlois' reagent (NaSO2CF3), and (iv) the kinetic study of the developed methodology. The strategy exhibits broad substrate scope and scalability, making it practical. Installation of generated azetidines into marketed drug motifs, including ibuprofen, naproxen, and olaparib derivative, demonstrates the method's utility. Mechanistic investigations, supported by control experiments, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS), provided key insights into the reaction pathway. This electrochemical approach advances the strain-release chemistry of ABBs and offers a promising platform for future developments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":"e5707597"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753105","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

Rational Design of a {InCu6} Heterometallic Oxo Cluster for Superior Proton Conduction: Mechanistic Insights and Humidity Gradient-Based Power Generation 用于优异质子传导的{InCu6}异金属氧簇的合理设计：机理见解和基于湿度梯度的发电

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.6584076

Yongzhen Chen, Yun-Zuo Cui, Yi Zhang, Rong-Lin Zhong, Qianqian Liu, Jiaxin Li, Zhong-Min Su, Hong-Ying Zang

{"title":"Rational Design of a {InCu6} Heterometallic Oxo Cluster for Superior Proton Conduction: Mechanistic Insights and Humidity Gradient-Based Power Generation","authors":"Yongzhen Chen, Yun-Zuo Cui, Yi Zhang, Rong-Lin Zhong, Qianqian Liu, Jiaxin Li, Zhong-Min Su, Hong-Ying Zang","doi":"10.1002/anie.6584076","DOIUrl":"https://doi.org/10.1002/anie.6584076","url":null,"abstract":"This study employs a template-directed assembly strategy to synthesize the first In3+/Cu2+ heterometallic oxo cluster, {InCu6}. {InCu6} costabilized by l-(+)-tartaric and acetic acids, features a central InO6 octahedron surrounded by six Cu2+ ions. Benchmarked against structurally analogous heterometallic oxo clusters, {InCu6} demonstrates superior proton conductivity of 7.95 × 10−2 S cm−1 at 30°C and 90% relative humidity (RH). DFT calculations indicate that the introduction of In3+ significantly reduces the energy barrier for proton detachment from the oxygen atoms in {InCu6}, thus elucidating the kinetic mechanism by which In3+/Cu2+ synergy enhances the conduction efficiency. To translate this molecular performance into a functional device for humidity gradient-based power generators (HGPGs), a novel cationic polymer (PVA-CTPP+Br−) was designed and synthesized as the matrix to form a uniform PVA-CTPP+-{InCu6} composite film. The resulting planar generator demonstrated stable performance, delivering an output of 0.63 V and 14.3 µA cm−2 at 92% RH and room temperature.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"153 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753077","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

Unexpected Spontaneous Photochemical Formation of Hydrogen Peroxide in Water Microdroplets on Silicate Mineral Surfaces. 硅酸盐矿物表面微水滴中过氧化氢的意外自发光化学形成。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.9633132

Haoran Yu,Longgang Chu,Zhaoyue Sun,Ruobing Wang,Xinghao Wang,Juan Gao,Davide Vione,Bing Wu,Hongqiang Ren,Joseph S Francisco,Cheng Gu

{"title":"Unexpected Spontaneous Photochemical Formation of Hydrogen Peroxide in Water Microdroplets on Silicate Mineral Surfaces.","authors":"Haoran Yu,Longgang Chu,Zhaoyue Sun,Ruobing Wang,Xinghao Wang,Juan Gao,Davide Vione,Bing Wu,Hongqiang Ren,Joseph S Francisco,Cheng Gu","doi":"10.1002/anie.9633132","DOIUrl":"https://doi.org/10.1002/anie.9633132","url":null,"abstract":"Hydrogen peroxide (H2O2) is a vital reactive oxygen species with significant roles in atmospheric and environmental chemistry. While its spontaneous generation in water microdroplets has gained attention, the abiotic pathways for its formation are still not fully understood. In this study, we demonstrate the rapid and spontaneous photochemical generation of H2O2 in pure water microdroplets on quartz surfaces under anoxic conditions. We show that H2O2 is efficiently formed through multiple pathways, including direct water photooxidation at the solid-water interface and, more significantly, reactions between water and quartz surface-bound peroxy radicals (≡Si-O-O·). The observed H2O2 production rate reached 2.5 × 1011 molecules cm- 2 s- 1 in microdroplets on quartz, exceeding that of bulk water photolysis by five orders of magnitude. This process occurs across various natural silicate minerals, suggesting that photochemical reactions in water microdroplets on silicate surfaces may represent a significant yet previously overlooked source of H2O2 in Earth's environment. Additionally, the solid-liquid interface reactions demonstrated in this study may offer a novel approach for the industrial-scale synthesis of H2O2, providing an efficient and sustainable alternative to traditional methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e9633132"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753087","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

Dual-Sabatier Optima: How Reaction Mechanism Determines Activity Volcano Map of Dual-Atom Catalysts for Oxygen Reduction Reaction. 双sabatier优化：反应机理如何决定氧还原反应双原子催化剂的活火山图。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.8386838

Jin Liu,Hao Li,Haoxiang Xu,Daojian Cheng

{"title":"Dual-Sabatier Optima: How Reaction Mechanism Determines Activity Volcano Map of Dual-Atom Catalysts for Oxygen Reduction Reaction.","authors":"Jin Liu,Hao Li,Haoxiang Xu,Daojian Cheng","doi":"10.1002/anie.8386838","DOIUrl":"https://doi.org/10.1002/anie.8386838","url":null,"abstract":"Dual-atom catalysts (DACs) have demonstrated superior potential in the oxygen reduction reaction (ORR). However, the single-peak activity volcano derived from classical associative mechanism is contrast to the large-scale experimental data from the Digital Catalysis Platform (DigCat). Herein, we studied ORR over 200 DACs from thermodynamic and kinetic perspectives, and found that the dissociative mechanism is generally dominant for DACs. By integrating potential-related microkinetic modeling and machine learning (ML)-derived interpretable structural descriptors, we discovered a dual-Sabatier optima volcano map against ΔG(OH*) (or structural descriptors), which was rigorously validated against available experimental data. Dual-Sabatier optima stem from the rate-determining step of dissociative mechanism switching among three elementary reactions (O2 dissociation → 2OH protonation → OH protonation), which can be extended across DACs containing transition metal, metal-like, and non-metal elements as center atoms. It opens a brand-new perspective for rational design of DACs and atomically dispersed catalysts for other reactions beyond ORR, of which the dominant reaction mechanism may be different from single-atom catalysts (SACs) and lead to diverse activity volcano maps. Most importantly, this work illustrates that new phenomenon can be identified from \"old experimental data\" under a large data scale, with the help of theoretical simulations integrated with interpretable ML.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":"e8386838"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751253","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

Multicomponent C-H Activation/Annulation Polymerizations Toward Structurally Regular Polyelectrolytes With Light-Boosted Antibacterial Potency. 多组分C-H活化/环状聚合制备具有光增强抗菌效力的结构规则聚电解质。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.5772470

Jiayang Li,Haiyan Huang,Jun Zhu,Dongyang Fan,Jinchuan Zhang,Xiaopeng Wang,Dong Wang,Ben Zhong Tang,Ting Han

{"title":"Multicomponent C-H Activation/Annulation Polymerizations Toward Structurally Regular Polyelectrolytes With Light-Boosted Antibacterial Potency.","authors":"Jiayang Li,Haiyan Huang,Jun Zhu,Dongyang Fan,Jinchuan Zhang,Xiaopeng Wang,Dong Wang,Ben Zhong Tang,Ting Han","doi":"10.1002/anie.5772470","DOIUrl":"https://doi.org/10.1002/anie.5772470","url":null,"abstract":"C-H activation/annulation polymerization (CAAP) has emerged as a powerful synthetic tool toward heteroaromatic polyelectrolytes, but its broader application is severely limited by the regioisomerization issues arising from the use of asymmetric diyne monomers. Access to structurally regular heteroaromatic polyelectrolytes via CAAP reactions is highly desirable yet remains challenging. In this study, we develop a one-pot multicomponent CAAP strategy that intrinsically circumvents regioisomerization by employing symmetric and monofunctional internal alkynes as comonomers to polymerize with aromatic dialdehydes and diamines. A series of structurally well-defined polyelectrolytes featuring multiaryl-substituted dibenzo[a,f]quinolizium units were in situ generated with high molecular weights (absolute Mw up to 224700 g/mol) in good yields (up to 91.2%). The resulting polyelectrolytes exhibited excellent solubility and readily tunable photophysical properties, with fluorescence emission extending to the first near-infrared region. Moreover, these structurally regular conjugated polyelectrolytes exhibit synergistic photothermal and photodynamic effects, achieving potent light-enhanced antibacterial and antibiofilm activities against both Gram-positive and Gram-negative bacteria, including drug-resistant strains. This work provides a versatile polymerization platform for the precise synthesis of diverse functional polyelectrolytes with promising applications in optoelectronics and antimicrobial therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"67 1","pages":"e5772470"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751244","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

Contra-Diffusion Engineering of Single-Atom Catalytic Interlayers Enables Reversible Sulfur Redox Chemistry 单原子催化中间层的反扩散工程实现可逆硫氧化还原化学

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.7009531

Yan-Jhang Chen, Tsung-I. Yeh, Chia-Yu Chang, Wei-Ming Huang, Jing-Yu Li, Mohamed Gamal Mohamed, Shiao-Wei Kuo, Bing-Joe Hwang, Yun-Sheng Ye

{"title":"Contra-Diffusion Engineering of Single-Atom Catalytic Interlayers Enables Reversible Sulfur Redox Chemistry","authors":"Yan-Jhang Chen, Tsung-I. Yeh, Chia-Yu Chang, Wei-Ming Huang, Jing-Yu Li, Mohamed Gamal Mohamed, Shiao-Wei Kuo, Bing-Joe Hwang, Yun-Sheng Ye","doi":"10.1002/anie.7009531","DOIUrl":"https://doi.org/10.1002/anie.7009531","url":null,"abstract":"Achieving durable lithium–sulfur batteries with minimal catalyst loading remains challenging, particularly for interlayer designs where catalytic efficiency is often compromised by nonuniform active-site utilization. Here we demonstrate that diffusion-regulated precursor growth enables the construction of atomically dispersed Co–Nx catalytic sites within a freestanding aramid nanofiber-derived carbon interlayer. By synchronizing the bidirectional diffusion of metal ions and ligands, this process enforces spatially confined nucleation and homogeneous precursor evolution, yielding a uniformly accessible single-atom catalytic architecture while preserving the intrinsic fibrous conduction network. The resulting interlayer simultaneously enhances polysulfide anchoring, accelerates bidirectional sulfur redox kinetics, and regulates Li2S nucleation and dissolution, as directly revealed by in situ Raman spectroscopy and electrochemical analyses. As a consequence, the system delivers exceptional cycling stability under high-rate operation despite a low Co loading, highlighting the importance of diffusion-regulated catalytic architectures for efficient sulfur redox regulation in lithium–sulfur batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753078","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

Mechanically Activated Luminescence in Polyurethanes Incorporating Calixarene Mechanophores. 含杯芳烃机械基团聚氨酯的机械活化发光。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.9927716

Lucia Visieri,Alessandro Casnati,Laura Baldini,José Augusto Berrocal

{"title":"Mechanically Activated Luminescence in Polyurethanes Incorporating Calixarene Mechanophores.","authors":"Lucia Visieri,Alessandro Casnati,Laura Baldini,José Augusto Berrocal","doi":"10.1002/anie.9927716","DOIUrl":"https://doi.org/10.1002/anie.9927716","url":null,"abstract":"The conformational properties of cone calix[4]arenes are exploited to develop the first example of a calixarene-based mechanoluminophore. By functionalizing the distal positions at the upper rim of a calix[4]arene with pyrene moieties, we produce a macrocycle incorporating two 1,6-bis(phenylethynyl)pyrene fluorophores. The flexibility of the calix[4]arene scaffold facilitates the formation of intramolecular ground-state excimers involving the pyrene units, as evidenced by 1H NMR and fluorescence spectroscopy. Incorporating the calixarene mechanoluminophore into linear polyurethanes yields uniform films that exhibit the characteristic pyrene excimer emission. When these films are stretched, either manually or using a universal tensile tester, a fluorescence shift from green-yellow to blue is observed under irradiation with UV light. Such fluorescence change is reversible and repeatable over numerous stress and release cycles. We attribute this behavior to conformational changes in the calix[4]arene triggered by mechanical force, and in particular to the temporary dissociation of the intramolecular pyrene excimers into pyrene monomers. Thus, the flexible calix[4]arene scaffold enables the reversible separation of the two fluorophores while preserving their spatial proximity. We propose that this design concept can provide general guidelines for creating supramolecular mechanophores free of intermolecular aggregation effects.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e9927716"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753103","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

Engineering Plasmon-Semiconductor Coupling in Spatially Ordered Supraparticles for Boosted Photocatalytic Hydrogen Evolution. 空间有序超粒子的工程等离子体-半导体耦合促进光催化析氢。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2026-04-27 DOI: 10.1002/anie.8359659

Wenlong Fu,Zhiyong Geng,Biao Jiang,Jie Huang,Shenghe Dong,Maochang Liu,Peng-Peng Wang

{"title":"Engineering Plasmon-Semiconductor Coupling in Spatially Ordered Supraparticles for Boosted Photocatalytic Hydrogen Evolution.","authors":"Wenlong Fu,Zhiyong Geng,Biao Jiang,Jie Huang,Shenghe Dong,Maochang Liu,Peng-Peng Wang","doi":"10.1002/anie.8359659","DOIUrl":"https://doi.org/10.1002/anie.8359659","url":null,"abstract":"Organizing distinct nanocomponents into spatially ordered architectures offers a powerful strategy to regulate light-matter interactions and enhance photocatalytic efficiency, yet remains largely underexplored. Herein, we report the bottom-up construction of colloidal supraparticles (SPs) comprising photocatalytic CdS-based and plasmonic Au nanoparticles (NPs), forming spatially ordered hybrid superstructures with tunable Au NP size and compositional ratios. The optimized CdSe@CdS-Au SPs achieve a hydrogen evolution rate of 160 mmol h-1 g-1 under visible light, representing a significant enhancement over the mixture of the same components and outperforming previously reported similar NP-based systems. Ultrafast spectroscopic analyses combined with finite element simulations reveal that spatial confinement facilitates plasmon-mediated interactions between Au and CdSe@CdS NPs, leading to enhanced plasmonic local electric fields and efficient plasmon-induced resonance energy transfer from Au to the semiconductor domains. These photophysical advantages collectively account for the markedly improved photocatalytic activity. This study demonstrates nanoscale spatial engineering as a versatile strategy for tailoring hybrid architectures toward high-efficiency solar-to-chemical energy conversion.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":"e8359659"},"PeriodicalIF":16.6,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751251","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