Malcolm R. P. George, Lobna A. Elsadek, Max Deering, Larissa Costa de Almeida, Jasper L. Tyler, Adam Noble, Valerie J. Paul, Hendrik Luesch, Craig P. Butts, Varinder K. Aggarwal
The unique potential of marine polyhydroxylated macrolides in chemical biology and drug discovery has long been constrained by their structural complexity and limited material availability, frustrating efforts in stereochemical assignment, synthesis, and mechanism‐of‐action elucidation. Here, we establish an integrated workflow, combining chemogenomic profiling, ultra‐high‐resolution NMR, and modular total synthesis, for the comprehensive functional and structural interrogation of this challenging natural product class. Applying this approach to caylobolides, natural products isolated from scarce samples of Okeania sp., we performed structure‐activity relationship studies revealing that acetylation at C29 markedly reduces both cytotoxicity and antifungal activity, pinpointing a key pharmacophore. Mechanistic profiling suggests that these macrolides disrupt membrane integrity, similar to amantelide A. Using natural compound samples, we simultaneously revised the structure of caylobolide B through 1 H, 1D‐selective TOCSY and HSQC NMR, and developed a modular fragment‐based synthesis of these compounds. By providing a unified methodology for genetic sensitivity profiling, precise structure and stereochemistry determination, and modular total synthesis, this work unlocks new opportunities for the discovery and rational design of potent marine‐derived therapeutics.
海洋多羟基大环内酯在化学生物学和药物发现方面的独特潜力长期受到其结构复杂性和有限的材料可用性的限制，在立体化学分配，合成和作用机制阐明方面的努力令人沮丧。在这里，我们建立了一个集成的工作流程，结合化学基因组分析、超高分辨率核磁共振和模块化全合成，对这类具有挑战性的天然产物进行全面的功能和结构分析。将这种方法应用于从稀有的Okeania sp.样品中分离的天然产物caylobolides，我们进行了结构-活性关系研究，揭示了C29的乙酰化显著降低了细胞毒性和抗真菌活性，确定了一个关键的药效团。机制分析表明，这些大环内酯类物质破坏了膜的完整性，类似于amantelide a .使用天然化合物样品，我们同时通过1h， 1D选择性TOCSY和HSQC NMR修改了caylobolide B的结构，并开发了基于模块化片段的合成这些化合物。通过提供遗传敏感性分析、精确结构和立体化学测定以及模块化全合成的统一方法，这项工作为发现和合理设计有效的海洋衍生疗法开辟了新的机会。
{"title":"Caylobolide B: Structure Revision, Total Synthesis, Biological Characterization, and Discovery of New Analogues","authors":"Malcolm R. P. George, Lobna A. Elsadek, Max Deering, Larissa Costa de Almeida, Jasper L. Tyler, Adam Noble, Valerie J. Paul, Hendrik Luesch, Craig P. Butts, Varinder K. Aggarwal","doi":"10.1002/anie.202523117","DOIUrl":"https://doi.org/10.1002/anie.202523117","url":null,"abstract":"The unique potential of marine polyhydroxylated macrolides in chemical biology and drug discovery has long been constrained by their structural complexity and limited material availability, frustrating efforts in stereochemical assignment, synthesis, and mechanism‐of‐action elucidation. Here, we establish an integrated workflow, combining chemogenomic profiling, ultra‐high‐resolution NMR, and modular total synthesis, for the comprehensive functional and structural interrogation of this challenging natural product class. Applying this approach to caylobolides, natural products isolated from scarce samples of <jats:italic>Okeania</jats:italic> sp., we performed structure‐activity relationship studies revealing that acetylation at C29 markedly reduces both cytotoxicity and antifungal activity, pinpointing a key pharmacophore. Mechanistic profiling suggests that these macrolides disrupt membrane integrity, similar to amantelide A. Using natural compound samples, we simultaneously revised the structure of caylobolide B through <jats:sup>1</jats:sup> H, 1D‐selective TOCSY and HSQC NMR, and developed a modular fragment‐based synthesis of these compounds. By providing a unified methodology for genetic sensitivity profiling, precise structure and stereochemistry determination, and modular total synthesis, this work unlocks new opportunities for the discovery and rational design of potent marine‐derived therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717444","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}
Sayad Doobary, Judith Braunreuther, Andrew K. Inge, Berit Olofsson
Densely functionalized alkenes are often utilized as excellent tools for further functionalization of molecules. Recent progress in their synthesis includes nucleophilic addition to vinylbenziodoxolones (VBX) and vinylbenziodoxoles (VBO) to reach alkenes with complete regio‐ and stereocontrol. In this work, we leverage the inherent properties of mechanochemistry to enable an efficient transition metal‐free one‐pot route to 1,2‐heteroatom‐substituted ( Z )‐alkenes directly from ethynylbenziodoxol(on)es (EBX/EBO), avoiding the isolation of VBX/VBO. We demonstrate a high‐yielding synthesis of a large variety of N/O/S ‐VBX reagents, which, combined with a telescoped nucleophilic addition, delivers a wide range of novel, complex ( Z )‐alkenes. This one‐pot strategy would be challenging to develop in solution due to a mismatch in reaction solvents, and the unique mechanochemical activation offered by solventless, solid‐state mixing also enables formation of products whose synthesis is inefficient with solvent‐based methods.
{"title":"Mechanochemical Synthesis of X ‐Vinylbenziodoxol(on)es and One‐Pot Conversion to Complex Alkenes **","authors":"Sayad Doobary, Judith Braunreuther, Andrew K. Inge, Berit Olofsson","doi":"10.1002/anie.202519049","DOIUrl":"https://doi.org/10.1002/anie.202519049","url":null,"abstract":"Densely functionalized alkenes are often utilized as excellent tools for further functionalization of molecules. Recent progress in their synthesis includes nucleophilic addition to vinylbenziodoxolones (VBX) and vinylbenziodoxoles (VBO) to reach alkenes with complete regio‐ and stereocontrol. In this work, we leverage the inherent properties of mechanochemistry to enable an efficient transition metal‐free one‐pot route to 1,2‐heteroatom‐substituted ( <jats:italic>Z</jats:italic> )‐alkenes directly from ethynylbenziodoxol(on)es (EBX/EBO), avoiding the isolation of VBX/VBO. We demonstrate a high‐yielding synthesis of a large variety of <jats:italic>N/O/S</jats:italic> ‐VBX reagents, which, combined with a telescoped nucleophilic addition, delivers a wide range of novel, complex ( <jats:italic>Z</jats:italic> )‐alkenes. This one‐pot strategy would be challenging to develop in solution due to a mismatch in reaction solvents, and the unique mechanochemical activation offered by solventless, solid‐state mixing also enables formation of products whose synthesis is inefficient with solvent‐based methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717442","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}
Solid polymer electrolytes (SPEs) emerge as prime candidates for next‐generation solid‐state lithium metal batteries, capitalizing on their intrinsic electrochemical robustness and enhanced safety profiles. However, overcoming the inherent trade‐off between efficient lithium‐salt dissociation and rapid ion migration remains a fundamental challenge for SPEs. We propose a programmable liquid crystal elastomer (LCE) framework with spatially patterned carbonyl (─C═O) and ether (─C─O─C─) oxygen motifs. In this hierarchical architecture, carbonyl groups act as stationary anchors to dissociate LiTFSI via strong coordination, while ether chains serve as dynamic relays enabling barrier‐reduced Li⁺ hopping along oriented mesophases. This decoupled “anchor‐relay” mechanism achieves outstanding room‐temperature performance: ionic conductivity of 4.05 × 10 −3 S cm −1 and Li⁺ transference number of 0.78. The synergistically induced LiF‐rich interphase further suppresses dendrite growth, the symmetric Li//Li cell exhibits a long‐term cycling lifespan over 1000 h with a low overpotential of 300 mV, delivering exceptional cycling stability in both LiFePO 4 //Li cell (90.1% capacity retention after 500 cycles) and high‐voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 //Li cell systems. The proposed LCEs as a transformative platform for next‐generation solid‐state batteries through rational molecular engineering.
固态聚合物电解质（spe）凭借其固有的电化学稳定性和更高的安全性，成为下一代固态锂金属电池的首选材料。然而，克服高效锂盐解离和快速离子迁移之间的内在权衡仍然是spe面临的一个基本挑战。我们提出了一个具有空间图案羰基（─C = O）和醚（─C─O─C─）氧基序的可编程液晶弹性体（LCE）框架。在这种分层结构中，羰基充当固定锚，通过强配位离解LiTFSI，而醚链充当动态中继，使屏障还原的Li +沿着定向中间相跳跃。这种解耦的“锚-继电器”机制实现了出色的室温性能：离子电导率为4.05 × 10−3 S cm−1，Li +的转移数为0.78。协同诱导的富liff间期进一步抑制了枝晶的生长，对称的Li//Li电池表现出超过1000小时的长期循环寿命和300 mV的低过电位，在lifepo4 //Li电池（500次循环后90.1%的容量保留）和高压LiNi 0.8 Co 0.1 Mn 0.1 o2 //Li电池系统中都具有出色的循环稳定性。通过合理的分子工程，提出LCEs作为下一代固态电池的变革性平台。
{"title":"Spatially Orchestrated Oxygen Motifs Decouple Ion Dissociation/Migration in Liquid Crystal Elastomer for High‐ Performance Solid‐State Li Metal Batteries","authors":"Zongcheng Miao, Rui Yan, Xingxing Zhang, Haiyan Bai, Fan Xi, Jinqi Chen, Zemin He, Shixue Dou","doi":"10.1002/anie.202522322","DOIUrl":"https://doi.org/10.1002/anie.202522322","url":null,"abstract":"Solid polymer electrolytes (SPEs) emerge as prime candidates for next‐generation solid‐state lithium metal batteries, capitalizing on their intrinsic electrochemical robustness and enhanced safety profiles. However, overcoming the inherent trade‐off between efficient lithium‐salt dissociation and rapid ion migration remains a fundamental challenge for SPEs. We propose a programmable liquid crystal elastomer (LCE) framework with spatially patterned carbonyl (─C═O) and ether (─C─O─C─) oxygen motifs. In this hierarchical architecture, carbonyl groups act as stationary anchors to dissociate LiTFSI via strong coordination, while ether chains serve as dynamic relays enabling barrier‐reduced Li⁺ hopping along oriented mesophases. This decoupled “anchor‐relay” mechanism achieves outstanding room‐temperature performance: ionic conductivity of 4.05 × 10 <jats:sup>−3</jats:sup> S cm <jats:sup>−1</jats:sup> and Li⁺ transference number of 0.78. The synergistically induced LiF‐rich interphase further suppresses dendrite growth, the symmetric Li//Li cell exhibits a long‐term cycling lifespan over 1000 h with a low overpotential of 300 mV, delivering exceptional cycling stability in both LiFePO <jats:sub>4</jats:sub> //Li cell (90.1% capacity retention after 500 cycles) and high‐voltage LiNi <jats:sub>0.8</jats:sub> Co <jats:sub>0.1</jats:sub> Mn <jats:sub>0.1</jats:sub> O <jats:sub>2</jats:sub> //Li cell systems. The proposed LCEs as a transformative platform for next‐generation solid‐state batteries through rational molecular engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717443","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}
Wen‐Bin Cao, Lingfei Hu, Jiaming Liu, George Chen, Gang Lu, Ming Chen
We report herein the development of catalytic asymmetric synthesis of secondary alkylboronates. Under the optimal conditions, Cu‐catalyzed semi‐reduction of 1‐alkyl‐ or 1,3‐dialkyl‐substituted 1‐boryl‐1,3‐butadienes forms secondary alkylboronates with excellent regioselectivities and enantioselectivities. With H 2 O as the source of hydrogen, the reaction proceeds through a protoboration and protodeboration cascade reaction sequence to generate the desired boronates. By using a slightly modified protocol, the process allows for access to enantioenriched deuterium‐labeled secondary alkylboronates. Density functional theory (DFT) studies were conducted to probe the origins of selectivities.
{"title":"Enantioselective Syntheses of Secondary Alkylboronates via Asymmetric Regioselective Reduction of 1,3‐Dienylboronates","authors":"Wen‐Bin Cao, Lingfei Hu, Jiaming Liu, George Chen, Gang Lu, Ming Chen","doi":"10.1002/anie.202517863","DOIUrl":"https://doi.org/10.1002/anie.202517863","url":null,"abstract":"We report herein the development of catalytic asymmetric synthesis of secondary alkylboronates. Under the optimal conditions, Cu‐catalyzed semi‐reduction of 1‐alkyl‐ or 1,3‐dialkyl‐substituted 1‐boryl‐1,3‐butadienes forms secondary alkylboronates with excellent regioselectivities and enantioselectivities. With H <jats:sub>2</jats:sub> O as the source of hydrogen, the reaction proceeds through a protoboration and protodeboration cascade reaction sequence to generate the desired boronates. By using a slightly modified protocol, the process allows for access to enantioenriched deuterium‐labeled secondary alkylboronates. Density functional theory (DFT) studies were conducted to probe the origins of selectivities.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717441","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}
Electrochemical separation technology offers an effective approach to recycle valuable nitrogen from industrial wastewater, but its separation efficiency is reduced by competitive electrostatic interactions from multiple ions. By engineering a competitive chemical reaction to facilitate site-specific electrochemical binding of NO3 -, this approach offers a promising route for high-efficiency anion separation in complex solutions. Herein, a novel [Bi2O2]2+ layered Faraday electrode was designed with two-dimensional channels for NO3 - migration and multiple sites that boost its interaction through combined electrostatic and coordination forces. In addition, by strategically introducing exogenous anions, the induced antisite cation defects at Bi3+ sites enhance the coordination of subsequent NO3 - insertion, achieving a NO3 - removal capacity of 182.47 mg g-1. Meanwhile, the highly charged CO3 2- enhances its repulsion against other competitive anions, leading to an impressive removal ratio of 90.78% for NO3 - in multi-ion solutions. More importantly, exogenous CO3 2- intercalation reverses the interlayer binding energy hierarchy between NO3 - and SO4 2-, converting the substitution by NO3 - (-13.12 eV) more thermodynamically favorable than that by SO4 2- (-12.16 eV), enabling spontaneous NO3 - uptake. Our work provides new insights for designing NO3 --selective electrodes, enhancing understanding of anion-interface interactions.
{"title":"Unlocking Selective Electrochemical Regulation via Interlayer Anion Competition for Nitrate Extraction from Wastewater.","authors":"Baixue Ouyang,Rui Huang,Peng Chen,Tingzheng Zhang,Dun Wei,Haoran Dong,Yuewen Qing,Yingjie He,Wenchao Zhang,Haiying Wang,Liyuan Chai","doi":"10.1002/anie.202522623","DOIUrl":"https://doi.org/10.1002/anie.202522623","url":null,"abstract":"Electrochemical separation technology offers an effective approach to recycle valuable nitrogen from industrial wastewater, but its separation efficiency is reduced by competitive electrostatic interactions from multiple ions. By engineering a competitive chemical reaction to facilitate site-specific electrochemical binding of NO3 -, this approach offers a promising route for high-efficiency anion separation in complex solutions. Herein, a novel [Bi2O2]2+ layered Faraday electrode was designed with two-dimensional channels for NO3 - migration and multiple sites that boost its interaction through combined electrostatic and coordination forces. In addition, by strategically introducing exogenous anions, the induced antisite cation defects at Bi3+ sites enhance the coordination of subsequent NO3 - insertion, achieving a NO3 - removal capacity of 182.47 mg g-1. Meanwhile, the highly charged CO3 2- enhances its repulsion against other competitive anions, leading to an impressive removal ratio of 90.78% for NO3 - in multi-ion solutions. More importantly, exogenous CO3 2- intercalation reverses the interlayer binding energy hierarchy between NO3 - and SO4 2-, converting the substitution by NO3 - (-13.12 eV) more thermodynamically favorable than that by SO4 2- (-12.16 eV), enabling spontaneous NO3 - uptake. Our work provides new insights for designing NO3 --selective electrodes, enhancing understanding of anion-interface interactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"240 1","pages":"e22623"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711078","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}
As prototypical organic electrochromic materials viologens have been extensively studied in display technologies, smart materials, and energy storage applications. Their properties can be fine-tuned by introducing different substituents on the pyridine rings, fusion with heteroatoms, or insertion of π–conjugated linkers. In this article we study the effect of B-N fused dipyridylanthracene (BDPA) as a novel linker unit in viologens on the electronic structure, optical properties, and electrochromic characteristics. Quaternization of pyridyl-functionalized BDPA (1Py) by N-methylation or complexation with B(C6F5)3 as a powerful Lewis acid gives rise to two fundamentally different π-extended viologens, dicationic [1Py-Me](PF6)2, and the neutral complex 1Py-BCF. We investigate the effect of these different quaternization methods on the LUMO energy, band gaps, absorption and emission, and the self-sensitized reactivity toward oxygen. We also demonstrate facile electrochemical reduction to singly and multiply reduced species. Spectroelectrochemical and computational studies reveal formation of strongly colored doubly reduced species with a closed shell electronic configuration and prominent quinoidal delocalization. The corresponding radical anions give rise to absorptions in the near-IR. A prototype electrochromic device with 1Py-BCF as the redox-active material is also presented.
{"title":"B-N Fused Anthracene as Functional Linker for π-Extended Viologens: Near-IR Emission and Electrochromism","authors":"Rajendra Prasad Nandi, Jingyao Zuo, Abhishek Shibu, Frieder Jäkle","doi":"10.1002/anie.202521634","DOIUrl":"https://doi.org/10.1002/anie.202521634","url":null,"abstract":"As prototypical organic electrochromic materials viologens have been extensively studied in display technologies, smart materials, and energy storage applications. Their properties can be fine-tuned by introducing different substituents on the pyridine rings, fusion with heteroatoms, or insertion of π–conjugated linkers. In this article we study the effect of B-N fused dipyridylanthracene (BDPA) as a novel linker unit in viologens on the electronic structure, optical properties, and electrochromic characteristics. Quaternization of pyridyl-functionalized BDPA (<b>1Py</b>) by N-methylation or complexation with B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> as a powerful Lewis acid gives rise to two fundamentally different π-extended viologens, dicationic [<b>1Py-Me</b>](PF<sub>6</sub>)<sub>2</sub>, and the neutral complex <b>1Py-BCF</b>. We investigate the effect of these different quaternization methods on the LUMO energy, band gaps, absorption and emission, and the self-sensitized reactivity toward oxygen. We also demonstrate facile electrochemical reduction to singly and multiply reduced species. Spectroelectrochemical and computational studies reveal formation of strongly colored doubly reduced species with a closed shell electronic configuration and prominent quinoidal delocalization. The corresponding radical anions give rise to absorptions in the near-IR. A prototype electrochromic device with <b>1Py-BCF</b> as the redox-active material is also presented.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"39 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711192","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}
Carlo Gericke, Edmondo M. Benetti, Barbara Fresch, Cristian Pezzato
Spiropyran-based polymers are widely studied on account of their multifaceted stimuli-responsive behaviors. However, their photoacid characteristics in aqueous environments remain overlooked. Here, we synthesized a series of poly(3-sulfopropyl methacrylate) copolymers containing spiropyran units in their photoacidic, protonated merocyanine form. We studied the behavior of these copolymer polyelectrolytes in water and found that polymer constitution significantly enhances the hydrolytic stability of protonated merocyanines, whereas polymer composition can be used as a tool to program their photoacidity – i.e., the acidity difference between their ground state and metastable state. Exposure to 500 nm light enables these polyelectrolytes to reversibly dissociate protons, causing metastable fluctuations in bulk pH as large as 3 pH units. The results presented here hold promise in the development of robust light-to-protonic energy conversion devices.
{"title":"Stimuli-Responsive Photoacid Polyelectrolytes","authors":"Carlo Gericke, Edmondo M. Benetti, Barbara Fresch, Cristian Pezzato","doi":"10.1002/anie.202519930","DOIUrl":"https://doi.org/10.1002/anie.202519930","url":null,"abstract":"Spiropyran-based polymers are widely studied on account of their multifaceted stimuli-responsive behaviors. However, their photoacid characteristics in aqueous environments remain overlooked. Here, we synthesized a series of poly(3-sulfopropyl methacrylate) copolymers containing spiropyran units in their photoacidic, protonated merocyanine form. We studied the behavior of these copolymer polyelectrolytes in water and found that polymer constitution significantly enhances the hydrolytic stability of protonated merocyanines, whereas polymer composition can be used as a tool to program their photoacidity – i.e., the acidity difference between their ground state and metastable state. Exposure to 500 nm light enables these polyelectrolytes to reversibly dissociate protons, causing metastable fluctuations in bulk pH as large as 3 pH units. The results presented here hold promise in the development of robust light-to-protonic energy conversion devices.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"39 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711252","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}
High‐energy‐density lithium–sulfur batteries exhibit obvious kinetics differences involving multistep reactions, making it hard to realize constantly high‐efficient polysulfide conversion during the full charging/discharging Herein, we propose a concept of Li + ‐respiration‐effect‐induced cascade catalysis through taking full advantage of dynamic active sites from in situ potential‐modulated TiNb 2 O 7 . The Li + respiration effect activates the lattice O atom and regulates the antibonding orbitals filling, triggering an electrochemical‐dominated switchable catalytic for sequential conversion of intermediates. As a result, the Li–S cell displays a good cycling stability and wide‐temperature ability from −30 to +60 °C. A flexible pouch cell maintains a capacity retention of 94.6% after 120 cycles. Our discovery provides a fire‐new perspective in electrochemically reconstructed catalysis for wide‐temperature‐tolerant Li − S batteries.
{"title":"Dynamic Li + Respiration Effect Enables Cascade Conversion of Lithium Polysulfides for Li–S Batteries","authors":"Yan Zhang, Wei Zhao, Yanbin Ning, Shenglu Geng, Shengwei Dong, Chong Wang, Fei Sun, Geping Yin, Shuaifeng Lou","doi":"10.1002/anie.202524645","DOIUrl":"https://doi.org/10.1002/anie.202524645","url":null,"abstract":"High‐energy‐density lithium–sulfur batteries exhibit obvious kinetics differences involving multistep reactions, making it hard to realize constantly high‐efficient polysulfide conversion during the full charging/discharging Herein, we propose a concept of Li <jats:sup>+</jats:sup> ‐respiration‐effect‐induced cascade catalysis through taking full advantage of dynamic active sites from in situ potential‐modulated TiNb <jats:sub>2</jats:sub> O <jats:sub>7</jats:sub> . The Li <jats:sup>+</jats:sup> respiration effect activates the lattice O atom and regulates the antibonding orbitals filling, triggering an electrochemical‐dominated switchable catalytic for sequential conversion of intermediates. As a result, the Li–S cell displays a good cycling stability and wide‐temperature ability from −30 to +60 °C. A flexible pouch cell maintains a capacity retention of 94.6% after 120 cycles. Our discovery provides a fire‐new perspective in electrochemically reconstructed catalysis for wide‐temperature‐tolerant Li − S batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"93 1","pages":"e24645"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711355","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}
Engineering structural distortions presents a powerful strategy for tailoring the optoelectronic properties of luminescent materials, while a fundamental understanding of how atomic‐scale distortions govern photoluminescence in copper‐iodide clusters has remained elusive. Herein, we report a model van der Waals solid based on copper–iodide clusters, where two vertically oriented and alternately arranged [Cu 2 I 4 ] 2− clusters are assembled via protection and interaction afforded by peripheral long‐alkyl‐chain cetyltrimethylammonium bromide ligands. This unique architecture affords a cooperative distortion response and exceptional buffering capacity, enabling precise control and direct probing of atomic‐scale structural distortions under pressure. We demonstrate that hydrostatic pressure induces controlled atomic distortions and an isostructural phase transition, which collectively enhance exciton localization. This leads to a dramatic amplification of self‐trapped emission, boosting the photoluminescence quantum yield from 32.25% to near‐unity (99.82%). Our work establishes atomic‐distortion engineering as a general principle for achieving ultimate control over light emission in hybrid semiconductors.
{"title":"Atomic‐Scale Structural Distortion Drives Exciton Localization for Near‐Unity Photoluminescence in Copper–Iodide Clusters","authors":"Haifeng Zhu, Shengrong He, Zhihao Xiao, Guangming Niu, Yanxue Yin, Shengqiao Wang, Laizhi Sui, Xinyi Yang, Bo Zou, Lijun Zhang, Zhennan Wu, Yu Zhang, Xue Bai","doi":"10.1002/anie.202522640","DOIUrl":"https://doi.org/10.1002/anie.202522640","url":null,"abstract":"Engineering structural distortions presents a powerful strategy for tailoring the optoelectronic properties of luminescent materials, while a fundamental understanding of how atomic‐scale distortions govern photoluminescence in copper‐iodide clusters has remained elusive. Herein, we report a model van der Waals solid based on copper–iodide clusters, where two vertically oriented and alternately arranged [Cu <jats:sub>2</jats:sub> I <jats:sub>4</jats:sub> ] <jats:sup>2−</jats:sup> clusters are assembled via protection and interaction afforded by peripheral long‐alkyl‐chain cetyltrimethylammonium bromide ligands. This unique architecture affords a cooperative distortion response and exceptional buffering capacity, enabling precise control and direct probing of atomic‐scale structural distortions under pressure. We demonstrate that hydrostatic pressure induces controlled atomic distortions and an isostructural phase transition, which collectively enhance exciton localization. This leads to a dramatic amplification of self‐trapped emission, boosting the photoluminescence quantum yield from 32.25% to near‐unity (99.82%). Our work establishes atomic‐distortion engineering as a general principle for achieving ultimate control over light emission in hybrid semiconductors.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"78 1","pages":"e22640"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711354","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}
The dynamic inversion of circularly polarized luminescence (CPL) in solid‐state materials is a pivotal goal for both fundamental science and advanced chiroptoelectronic technologies. While achievable in flexible molecular systems, CPL inversion remains profoundly challenging in crystalline lattices due to their inherent structural rigidity. Herein, we demonstrate irreversible CPL inversion in a single crystal of a lead‐based hybrid metal halide, P / M ‐(C 4 H 14 S 2 N 2 )PbBr 5 ·H 3 O ( P / M ‐PbBr), engineered with stereochemically dynamic cysteamine cations. The inversion is achieved by applying a magnetic field at a specific phase transition temperature (486 K), which triggers a magneto‐thermal‐induced structural transformation that flips the crystal's absolute chirality between its P and M enantiomeric forms. This configurational reversal of the organic moieties drives a cooperative structural inversion of the entire inorganic lattice, thereby switching the CPL handedness. Our work provides a fundamental strategy for achieving chirality control in rigid crystalline systems, paving the way for developing programmable chiroptical materials and devices.
{"title":"Irreversible Inversion of Circularly Polarized Luminescence via Magneto‐Thermal‐Induced Structural Reorganization in a Chiral Lead Bromide Crystal","authors":"Yulian Liu, Yiyang Wang, Peijie Zhang, Xiaofan Xu, Sixia Hu, Zewei Quan","doi":"10.1002/anie.202521709","DOIUrl":"https://doi.org/10.1002/anie.202521709","url":null,"abstract":"The dynamic inversion of circularly polarized luminescence (CPL) in solid‐state materials is a pivotal goal for both fundamental science and advanced chiroptoelectronic technologies. While achievable in flexible molecular systems, CPL inversion remains profoundly challenging in crystalline lattices due to their inherent structural rigidity. Herein, we demonstrate irreversible CPL inversion in a single crystal of a lead‐based hybrid metal halide, <jats:italic>P</jats:italic> / <jats:italic>M</jats:italic> ‐(C <jats:sub>4</jats:sub> H <jats:sub>14</jats:sub> S <jats:sub>2</jats:sub> N <jats:sub>2</jats:sub> )PbBr <jats:sub>5</jats:sub> ·H <jats:sub>3</jats:sub> O ( <jats:italic>P</jats:italic> / <jats:italic>M</jats:italic> ‐PbBr), engineered with stereochemically dynamic cysteamine cations. The inversion is achieved by applying a magnetic field at a specific phase transition temperature (486 K), which triggers a magneto‐thermal‐induced structural transformation that flips the crystal's absolute chirality between its <jats:italic>P</jats:italic> and <jats:italic>M</jats:italic> enantiomeric forms. This configurational reversal of the organic moieties drives a cooperative structural inversion of the entire inorganic lattice, thereby switching the CPL handedness. Our work provides a fundamental strategy for achieving chirality control in rigid crystalline systems, paving the way for developing programmable chiroptical materials and devices.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":"e21709"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711386","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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