Angewandte Chemie International Edition最新文献_第7页

Regioselective Nickel‐catalyzed Hydroarylation of gem‐Difluoroalkenes for the Synthesis of the ArCF2‐ Moiety

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202424714

Xiangyu Chen, Ruitong Zhang, Yaxing Wu, Fei Wang, Chao Chen

引用次数: 0

Peripheral Engineering of Multiple‐Resonance Framework Targeting Efficient Organic Lasers

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504652

Chihaya Adachi, Tuul Tsagaantsooj, Xun Tang, Tao Zhang, Yi-Ting Lee, Rajat Walia, Xian-kai Chen

{"title":"Peripheral Engineering of Multiple‐Resonance Framework Targeting Efficient Organic Lasers","authors":"Chihaya Adachi, Tuul Tsagaantsooj, Xun Tang, Tao Zhang, Yi-Ting Lee, Rajat Walia, Xian-kai Chen","doi":"10.1002/anie.202504652","DOIUrl":"https://doi.org/10.1002/anie.202504652","url":null,"abstract":"Multiple‐resonance thermally activated delayed fluorescent (MR‐TADF) emitters have emerged as promising candidates for organic laser applications due to the potential for simultaneously achieving large oscillator strength and triplet utilization. In this study, we investigate the impact of peripheral tert‐butyl (t‐Bu)‐ and phenyl (Ph)‐substituents on the typical 9‐(phenylcarbazol‐3‐yl)‐9H‐carbazole‐3‐carbonitrile (CzBN) MR framework. While these modifications preserve the frontier molecular orbital distribution with large oscillator strengths, they significantly influence excited‐state dynamics and molecular aggregation at even low doping concentrations. Introducing Ph substituents extends the π‐conjugation extension of CzBN, promoting closer molecular packing, detrimental molecular aggregation, and significantly broadening the excited‐state absorption (ESA) band, which negatively impacts lasing performance. In contrast, CzBN‐tBu, incorporating t‐Bu groups as non‐conjugated substituents, demonstrated reduced molecular aggregation and a distinct separation between the ESA band and stimulated emission region. Consequently, the optimal distributed feedback lasing performance is achieved by CzBN‐tBu across various doping concentrations, resulting in the lowest lasing threshold of 3.4 µJ cm−2. These findings underscore the impact of inherent aggregation at low doping ratio on lasing activities, highlighting the crucial role of rational peripheral engineering in modulating molecular interactions and excited‐state dynamics, offering design strategies for developing MR lasing molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736747","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

Modulating the Chromophores of Metal-Covalent Organic Frameworks for Boosting Low-Concentration CO2 Photoreduction

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202505292

Chong-Jiu Lu, Ji-Hong Zhang, Jian-Hua Mei, Yun-Nan Gong, Tong-Bu Lu, Di-Chang Zhong

{"title":"Modulating the Chromophores of Metal-Covalent Organic Frameworks for Boosting Low-Concentration CO2 Photoreduction","authors":"Chong-Jiu Lu, Ji-Hong Zhang, Jian-Hua Mei, Yun-Nan Gong, Tong-Bu Lu, Di-Chang Zhong","doi":"10.1002/anie.202505292","DOIUrl":"https://doi.org/10.1002/anie.202505292","url":null,"abstract":"The development of efficient photocatalysts to convert low-concentration CO2 into the value-added chemicals and fuels is particularly interesting yet remains highly challenging. Herein, we designed and synthesized three metal-covalent organic frameworks (MCOFs) through the Schiff-base condensation reactions between trinuclear copper complex and different BDP-based chromophores (BDP = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) for visible-light-driven reduction of low-concentration CO2 (15%) to HCOO-. As a result, MCOF-ANT containing anthracene (ANT) group achieves the highest HCOO- production rate of 1658 μmol g-1 h-1 (HCOO- selectivity, ~100%) in the absence of any additional noble-metal photosensitizers under a laboratory light source, which is 7.2 and 2.1 times higher than those of MCOF-Ph and MCOF-Nap with phenyl (Ph) and naphthalene (Nap) groups, respectively. Furthermore, MCOF-ANT also exhibits an excellent photocatalytic activity for the reduction of low-concentration CO2 (15%) to HCOO- under natural sunlight, with a HCOO- production rate of 1239 μmol g-1 h-1 (HCOO- selectivity, ~100%). Experiments and theoretical calculations reveal that the presence of ANT in MCOF-ANT is favorable to the visible-light harvesting and charge separation, as well as the formation of *OCO intermediate, which clearly accounts for its superior catalytic activity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737284","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

Cold-Optimized Zinc-Ion Batteries: Enhanced Stability at -5°C 低温优化锌离子电池：增强零下 5°C 的稳定性

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202503435

Jianming Meng, Yulai Lin, Yuqing Wang, Peng Hei, Ya Sai, Jing Wang, Xiaoqi Sun, Xiao-Xia Liu, Yu Song

{"title":"Cold-Optimized Zinc-Ion Batteries: Enhanced Stability at -5°C","authors":"Jianming Meng, Yulai Lin, Yuqing Wang, Peng Hei, Ya Sai, Jing Wang, Xiaoqi Sun, Xiao-Xia Liu, Yu Song","doi":"10.1002/anie.202503435","DOIUrl":"https://doi.org/10.1002/anie.202503435","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have been extensively studied under room and ultralow temperature conditions. However, mechanism studies at intermediate temperature ranges remain limited. In this work, we investigate the electrochemical performance of an AZIB using a commonly employed 3 M ZnSO4 electrolyte across the intermediate temperature range of 25 to -15 °C. Notably, we find that the battery with a double hydroxide cathode exhibits optimized performance at -5 °C, demonstrating significantly enhanced cycling stability compared to 25 °C. Mechanistic studies reveal that unfavorable H+-associated reactions at both the cathode and anode are effectively alleviated at -5 °C, contributing to improved cycling stability. Spectroscopic and theoretical analyses show that changes in the electrolyte environment at -5 °C—such as reduced electrochemical activity of H2O, increased H-bond strength, and decreased total number of H bonds—impede H+ diffusion through the H-bond network via the Grotthuss mechanism. These effects collectively suppress harmful H+-associated reactions, allowing Zn2+ insertion/de-insertion to dominate the charge storage process. This work provides valuable insights into the enhanced performance of AZIBs at sub-low temperatures and presents opportunities for extending battery operation in near-freezing environments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737287","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

Photo‐Self‐Fenton Reaction Mediated by Silver Single Atom and Cluster Photocatalysts for Highly Selective Generation of Singlet Oxygen toward Efficient Organic Wastewater Treatment

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504028

Di Luo, Han Xiao, Yupeng Yang, Jiaxing Li, Yixing Wang, Xiaoru Huang, Mixuan Zhang, Lihui Wang, Jiarui Yang, Jiangzhi Zi, Zichao Lian, Guisheng Li, Hexing Li

{"title":"Photo‐Self‐Fenton Reaction Mediated by Silver Single Atom and Cluster Photocatalysts for Highly Selective Generation of Singlet Oxygen toward Efficient Organic Wastewater Treatment","authors":"Di Luo, Han Xiao, Yupeng Yang, Jiaxing Li, Yixing Wang, Xiaoru Huang, Mixuan Zhang, Lihui Wang, Jiarui Yang, Jiangzhi Zi, Zichao Lian, Guisheng Li, Hexing Li","doi":"10.1002/anie.202504028","DOIUrl":"https://doi.org/10.1002/anie.202504028","url":null,"abstract":"The persistent organic pollutants in wastewater have caused the heavy threat to ecosystems and humans, but selective removal of these pollutants still faces challenges due to low efficiency, extra addition of oxidation agents and many highly toxic intermediate products. Herein, we report an efficient fast kinetic conversion via a photo‐self‐Fenton‐like system of *OOH intermediate‐involved oxidation pathway with high selection generation of singlet oxygen (1O2) from the novel in‐situ H2O2 heterolytic activation route for the first time. The single‐atom and cluster doped zinc oxide (AgSA‐AgC/ZnO) was successfully synthesized to achieve the 100 % degradation yield and 80 % total of carbon (TOC) of the p‐chlorophenol (4‐CP) as the typical pollutant under solar‐light irradiation and exhibit long‐term activity in a self‐design photo‐Filter reactor for 4‐CP degradation. It was attributed to the accelerated cycles from Aghighδ+ site to Aglowδ+ site in Fenton‐like catalysis achieving the rapid selection conversion from the H2O2 heterolytic cleavage to ~100 % 1O2 via the intermediate *OOH at the Ag SA sites for ring‐opening reaction and reactive H* at the Ag clusters sites for dechlorination reaction, respectively. This discovery gives the deep understanding of the high‐performance photo‐self‐Fenton reaction through in‐situ cycles of variable metals for the organic contaminants treatment.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"58 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736746","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

Constructing Robust Electrode/Electrolyte Interphases for Highly Stable Lithium–Sulfurized Polyacrylonitrile Batteries

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202503214

Siyuan Shao, Jinze Hou, Youxuan Ni, Chunyan Zhu, Shuang Wu, Xinyi Liu, Can Wang, Kai Zhang, Zhenhua Yan, Yong Lu, Jun Chen

{"title":"Constructing Robust Electrode/Electrolyte Interphases for Highly Stable Lithium–Sulfurized Polyacrylonitrile Batteries","authors":"Siyuan Shao, Jinze Hou, Youxuan Ni, Chunyan Zhu, Shuang Wu, Xinyi Liu, Can Wang, Kai Zhang, Zhenhua Yan, Yong Lu, Jun Chen","doi":"10.1002/anie.202503214","DOIUrl":"https://doi.org/10.1002/anie.202503214","url":null,"abstract":"Lithium–sulfurized polyacrylonitrile (SPAN) batteries show great promise for energy storage, but are plagued by poor cycling stability, which can be attributed to unfavorable electrode/electrolyte interphases for both anode and cathode. Here we design and achieve the anion‐moderate solvation structure based interconnected clusters in electrolyte by regulating the interactions of solvent with Li+ and diluent to construct robust anode/electrolyte and cathode/electrolyte interphases simultaneously for high‐performance Li–SPAN batteries. The optimal electrolyte endows Li plating/stripping with a high Coulombic efficiency of 99.47% at 1 mA cm–2 in Li||Cu cells. The Li–SPAN batteries show excellent cycling stability with a high capacity retention of 94.21% after 1215 cycles. Moreover, the assembled pouch‐type Li–SPAN battery under limited electrolyte condition (2.40 g Ah–1) achieves a capacity of 3.75 Ah, corresponding to a high energy density of 180 Wh kg–1 based on the total mass of the battery. This work provides a good electrolyte design principle to construct robust anode/electrolyte and cathode/electrolyte interphases for batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"72 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745018","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

Controlling the chirality of Metallo-cages by Manipulating the Stereochemistry of the Metal Centers 通过操纵金属中心的立体化学来控制金属笼的手性

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202503833

Yu-Qing Li, Lei Fu, Zhiyuan Jiang, Ermeng Han, Tian Li, Qixia Bai, Ting-Zheng Xie, Zhe Zhang, Pingshan Wang, Tun Wu

{"title":"Controlling the chirality of Metallo-cages by Manipulating the Stereochemistry of the Metal Centers","authors":"Yu-Qing Li, Lei Fu, Zhiyuan Jiang, Ermeng Han, Tian Li, Qixia Bai, Ting-Zheng Xie, Zhe Zhang, Pingshan Wang, Tun Wu","doi":"10.1002/anie.202503833","DOIUrl":"https://doi.org/10.1002/anie.202503833","url":null,"abstract":"Precise control over the chirality of metallo-cages by maniplating the stereochemistry of metal centers is important in many practical applications, but is extremely challenging. In this study, two isostructural metallo-cuboctahedra (1-ZnII12L18 and 2-CdII12L18) have been assembled using ligand L1 and two kinds of metal ions (ZnII and CdII) with similar coordination lability. The chiral-induction by the same guests (D-/L-camphorsulfonate, D-/L-SCS) results in a completely opposing stereochemical output of 1 and 2: D-SCS induced host-guest complex of [D-SCS⊂Δ12-1] and [D-SCS⊂Λ12-2], respectively, with reverse handedness. The distinct stereochemical configuration of metallo-cuboctahedra can be manipulated by participant metal ions that exhibit similar dynamics. Furthermore, a subtle variation of the ligand peripheral substituent group facilitates spontaneous resolution of metallo-cuboctahedra 3-ZnII12L28 from a racemic mixture as (R24, Λ12)-3/(S24, Δ12)-3 enantiopure entities. The dynamic stereochemistry of MII12L8 cuboctahedra described in this work allows a chiral manipulation based on the nature of metal centers and ligands, enabling the design and control of the chirality of metallo-cages.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"216 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737288","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

Zwitterionic Dipeptide Surface Functionalization of Detonation Nanodiamond for Enhanced Control in Biological Environments

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202501202

Elisabeth Mayerhoefer, Himalaya Parajuli, Mihaela-Roxana Cimpan, Daniela Elena Costea, Harsh Nitin Dongre, Anke Krueger

{"title":"Zwitterionic Dipeptide Surface Functionalization of Detonation Nanodiamond for Enhanced Control in Biological Environments","authors":"Elisabeth Mayerhoefer, Himalaya Parajuli, Mihaela-Roxana Cimpan, Daniela Elena Costea, Harsh Nitin Dongre, Anke Krueger","doi":"10.1002/anie.202501202","DOIUrl":"https://doi.org/10.1002/anie.202501202","url":null,"abstract":"Utilizing nanoparticles as innovative theranostic agents for biomedical applications requires full control over the material’s properties to dictate their interactions within a biological environment. Owing to its versatile surface chemistry and high biocompatibility, nanodiamond (ND) represents a promising platform for novel healthcare treatments. To ensure the performance and safety of NDs, their properties and behavior must remain unchanged upon administration, a key challenge in nanomedicine. Recently, zwitterionic surface modifications have emerged as new strategies to substantially improve protein‐repelling properties and biocompatibility of nanomaterials. Using for the first time covalently conjugated zwitterionic dipeptides as surface modulators for ND particles, we were able to provide a readily accessible, reproducible and tunable functionalization. The obtained particles demonstrate enhanced colloidal stability and conservation of particle size over a broad pH range and in different protein‐containing media compared to the starting material. By simple selection of different dipeptides, we can carefully tailor the biocompatibility and cellular uptake of functionalized NDs. We reveal the functionalized NDs’ behavior in biologically relevant 3D organotypic models and how different dipeptide functionalized NDs interact with squamous epithelium ex‐vivo. The results pave the way for various applications, e.g., biosensing, tissue engineering or targeted drug delivery of these highly biologically suitable nanoparticles.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"33 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736743","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

Removing α‐H in Carboxylate‐based Electrolytes for Stable Lithium Metal Batteries

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202503616

Yi Yang, Le-Geng Yu, Yu-Xin Huang, Xiao-Qing Ding, Zhou-Qing Xue, Zeheng Li, Yu-Xing Yao, Shuo Zhang, Lei Xu, Xue-Fei Wen, Jian Pei, Chong Yan, Jia-Qi Huang

{"title":"Removing α‐H in Carboxylate‐based Electrolytes for Stable Lithium Metal Batteries","authors":"Yi Yang, Le-Geng Yu, Yu-Xin Huang, Xiao-Qing Ding, Zhou-Qing Xue, Zeheng Li, Yu-Xing Yao, Shuo Zhang, Lei Xu, Xue-Fei Wen, Jian Pei, Chong Yan, Jia-Qi Huang","doi":"10.1002/anie.202503616","DOIUrl":"https://doi.org/10.1002/anie.202503616","url":null,"abstract":"Although carboxylate esters greatly improve the cold weather performance of graphite‐based lithium‐ion batteries utilized in arctic expeditions, the underlying cause of the incompatibility between carboxylates and lithium (Li) anodes has not been sufficiently explained, resulting in the greatly restricted usage of carboxylate in lithium metal batteries (LMBs). Herein, we reveal the serious parasitic reactions between carboxylate α‐H atoms and Li metal are the culprits that render carboxylate‐based ineffectiveness for LMBs. By replacing all α‐H atoms with fluorine atoms and methyl groups, we successfully construct inert carboxylates and find the ions/molecules distribution in electric‐double‐layer (EDL) can be manipulated at a molecular‐level. The unique structure ensuring more anions are positioned closer to the Li surface in the EDL of the inert carboxylate‐based electrolyte, the morphology of the deposited Li is significantly regulated and the chemical corrosion gets effectively inhibited. As a consequence of remarkable extending lifespan of carboxylate‐based LMBs with routine salt concentration and few additives. More generally, using carboxylates lacking α‐H atoms offers a realistic approach to increase the variety of solvents that can be used in LMBs electrolytes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"38 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736768","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

Isolable Three‐coordinate Base‐Stabilized Alumylene: A Precursor of Persistent Acceptor‐Free Monomeric Aluminum Oxide

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202505181

José Miguel Léon Baeza, Huihui Xu, Shintaro Takahashi, Antoine Baceiredo, Rene Segundo Rojas Guerrero, Daisuke Hashizume, Nathalie Saffon-Merceron, Vicenç Branchadell, Tsuyoshi Kato

引用次数: 0