Angewandte Chemie最新文献_第6页

Regiospecific Halogenation Modulates Molecular Dipoles in Self-Assembled Monolayers for High-Performance Organic Solar Cells 区域特定卤化调节高性能有机太阳能电池自组装单层中的分子偶极子

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202502215

Wenlin Jiang, Yanxun Li, Huanhuan Gao, Lingchen Kong, Chun-To Wong, Xi Yang, Francis R. Lin, Alex K.-Y. Jen

{"title":"Regiospecific Halogenation Modulates Molecular Dipoles in Self-Assembled Monolayers for High-Performance Organic Solar Cells","authors":"Wenlin Jiang, Yanxun Li, Huanhuan Gao, Lingchen Kong, Chun-To Wong, Xi Yang, Francis R. Lin, Alex K.-Y. Jen","doi":"10.1002/ange.202502215","DOIUrl":"https://doi.org/10.1002/ange.202502215","url":null,"abstract":"Halogenated carbazole-derived self-assembled monolayers (SAMs) are promising hole-extraction materials in conventional organic solar cells (OSCs). While halogenation helps optimize the molecular dipole, intermolecular interactions, and energetics of SAM, the highly polarizable carbon-halogen bonds can be reactive and prone to photocleavage depending on their regiochemistry. Herein, we study the regiospecific properties, including the intrinsic stability, electrostatic potential (ESP) distribution, and changes in molecular dipole of the brominated SAM molecules by brominating a helical 7H-dibenzo[c,g]carbazole-based SAM (CbzNaph) featuring a stronger dipole. Additionally, a correlation between the intrinsic molecular stability and the derived SAM surface stability is established to determine the performance and stability of the OSCs. Notably, the bromination at the chemically inert sites of 7H-dibenzo[c,g]carbazole (JJ26) helps maximize molecular dipole while maintaining superior intrinsic stability. Together with dense assembly promoted by the synergistically enhanced intermolecular interactions and crystallinity, JJ26 can efficiently modulate the work function (WF) of indium tin oxide (ITO) and enhance the stability of SAM under external stress. Consequently, the JJ26 derived OSC shows significantly improved performance, achieving an efficiency of 19.35% along with notably enhanced stability. This work shows that the precise modulation of the regiochemistry of SAM molecules is critical for improving their quality and derived device performance.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced Luminance of Pentaazaphenalene-Based Delayed Fluorescence Emitters by Breaking Forbidden Transition 打破禁跃迁增强五氮苯基延迟荧光发射体的亮度

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202504390

Yuka Yasuda, Katsuyuki Shizu, Hiroyuki Tanaka, Hironori Kaji

{"title":"Enhanced Luminance of Pentaazaphenalene-Based Delayed Fluorescence Emitters by Breaking Forbidden Transition","authors":"Yuka Yasuda, Katsuyuki Shizu, Hiroyuki Tanaka, Hironori Kaji","doi":"10.1002/ange.202504390","DOIUrl":"https://doi.org/10.1002/ange.202504390","url":null,"abstract":"1,3,4,6,9b-pentaazaphenalene (5AP) derivatives are of growing interest because of their potential for exhibiting thermally activated delayed fluorescence and inverted singlet–triplet excited state properties. However, a major challenge has been the nonemissive nature of 5AP. This study reports a donor-5AP-acceptor-type molecular design for converting nonemissive 5AP into highly emissive molecules. The newly designed molecules, 2,5-di(1-pyrrolidino)-7,9-bis(4-(trifluoromethyl)phenyl)-1,3,4,6,9b-pentaazaphenalene (Pyr-5AP-CF3) and 2,5-di(1-pyrrolidino)-7,9-bis(4-benzonitrile)-1,3,4,6,9b-pentaazaphenalene (Pyr-5AP-CN), exhibited delayed fluorescence and achieved high photoluminescence quantum yields of 83.5% and 90.6%, respectively, in solid films. These values dramatically exceed those of previously reported 5AP derivatives with only 8% or less. Furthermore, Pyr-5AP-CF3 and Pyr-5AP-CN exhibited the fastest radiative decays and the narrowest emission spectra among all the 5AP based materials reported to date. This study provides a promising solution to the nonemissive nature of 5AP, leading to the development of a class of highly luminescent materials for future organic light-emitting diodes.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Bench-Stable Fluorophosphine Nickel(0) Complex and Its Catalytic Application 一种稳定的氟膦镍配合物及其催化应用

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202506271

Franziska Flecken, Arjun Neyyathala, Toni Grell, Schirin Hanf

引用次数: 0

Highly Selective Oxygen Electroreduction to Hydrogen Peroxide on Sulfur-Doped Mesoporous Carbon 硫掺杂介孔碳上高选择性氧电还原制过氧化氢

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202503385

Juan Du, Yicheng Liu, Ming Sun, Jing Guan, Aibing Chen, Buxing Han

{"title":"Highly Selective Oxygen Electroreduction to Hydrogen Peroxide on Sulfur-Doped Mesoporous Carbon","authors":"Juan Du, Yicheng Liu, Ming Sun, Jing Guan, Aibing Chen, Buxing Han","doi":"10.1002/ange.202503385","DOIUrl":"https://doi.org/10.1002/ange.202503385","url":null,"abstract":"As a paradigm-shifting material platform in energy catalysis, precisely engineered ordered mesoporous carbon spheres emerge as supreme metal-free electrocatalysts, outperforming conventional carbon-based counterparts through synergistic structural and electronic innovations. Herein, we architecturally design vertically aligned cylindrical mesoporous carbon spheres with atomic-level sulfur doping (S-mC) that establish unprecedented performance benchmarks in the two-electron oxygen reduction reaction (2e−-ORR) to hydrogen peroxide. Systematic comparative studies reveal that the S-mC catalysts achieve exceptional H2O2 selectivity (>99%) and activity at current density of −3.5 mA cm−2, surpassing state-of-the-art metal-free catalysts in current density. Impressively, the optimized S-mC electrocatalyst in a flow cell device achieves an exceptional H2O2 yield of 25 mol gcatalyst−1 h−1. The carbon matrix's unique sp2/sp3 hybrid network coupled with S-induced charge redistribution generates electron-deficient hotspots that selectively stabilize *OOH intermediates, as evidenced by in situ spectroscopic characterization and DFT calculations. This structural–electronic synergy endows the carbon framework with metal-like catalytic efficiency while maintaining inherent advantages of chemical robustness and cost-effectiveness. The marriage of S-doping engineering with mesoscopic pore architecture control opens a new way for developing efficient carbon-based electrocatalysts for oxygen selective reduction to H2O2.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Efficient Semitransparent Organic Solar Modules with Exceptional Diurnal Stability Through Asymmetric Interaction Induced by Symmetric Molecular Structure 通过对称分子结构诱导的不对称相互作用，具有特殊日稳定性的高效半透明有机太阳能组件

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202424287

Sangjin Yang, Xuexiang Huang, Yongjoon Cho, Sungmo Koo, Yanni Ouyang, Zhe Sun, Seonghun Jeong, Thi Le Huyen Mai, Wonjun Kim, Lian Zhong, Shanshan Chen, Chunfeng Zhang, Hee-Seung Lee, Seong-Jun Yoon, Lie Chen, Changduk Yang

{"title":"Efficient Semitransparent Organic Solar Modules with Exceptional Diurnal Stability Through Asymmetric Interaction Induced by Symmetric Molecular Structure","authors":"Sangjin Yang, Xuexiang Huang, Yongjoon Cho, Sungmo Koo, Yanni Ouyang, Zhe Sun, Seonghun Jeong, Thi Le Huyen Mai, Wonjun Kim, Lian Zhong, Shanshan Chen, Chunfeng Zhang, Hee-Seung Lee, Seong-Jun Yoon, Lie Chen, Changduk Yang","doi":"10.1002/ange.202424287","DOIUrl":"https://doi.org/10.1002/ange.202424287","url":null,"abstract":"The symmetry-breaking design strategy of nonfullerene acceptor can improve the performance of semitransparent organic solar cells (ST-OSCs). However, no report exists on the “asymmetric molecular interaction” induced by symmetric molecular structure in nonfullerene acceptors. Herein, we showcase that 2D fluorophenyl outer groups in symmetric 4FY promote dipole-driven self-assembly through asymmetric molecular interactions, resulting in a tighter packed structure than Y6 with the same symmetric geometry. Such unique properties lead to high-performance layer-by-layer OSCs, accompanied by simultaneously reduced energy and recombination losses and improved charge-related characteristics. ST-OSCs based on PCE10-2F/4FY achieve notable power conversion efficiency (PCE) of 10.81%, average visible transmittance of 45.43%, and light utilization efficiency (LUE) of 4.91%. Moreover, exceptional diurnal cycling stability is observed in the ST-OSCs based on PCE10-2F/4FY with much prolonged T80 up to 134 h, which is about 17 times greater than the reference PCE10-2F/Y6. Lastly, we fabricate highly efficient semitransparent organic solar modules based on PCE10-2F/4FY (active area of 18 cm2), which shows PCE of 6.78% and the highest LUE of 3.10% to date for all-narrow bandgap semitransparent organic solar modules. This work demonstrates that asymmetry-driven molecular interactions can be leveraged to fabricate large-area ST-OSCs that are efficient and stable under realistic operating conditions.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202424287","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232324","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic Insights into the CO2-Assisted NO Electrochemical Deoxygenation and Hydrogenation co2辅助NO电化学脱氧加氢的机理研究

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202504499

Pan Li, Yi Liu, Liangyiqun Xie, Guangtao Wang, Xuanzhao Lu, Jian Li, Xuanhao Wu, Yujing Jiang, Wenlei Zhu

{"title":"Mechanistic Insights into the CO2-Assisted NO Electrochemical Deoxygenation and Hydrogenation","authors":"Pan Li, Yi Liu, Liangyiqun Xie, Guangtao Wang, Xuanzhao Lu, Jian Li, Xuanhao Wu, Yujing Jiang, Wenlei Zhu","doi":"10.1002/ange.202504499","DOIUrl":"https://doi.org/10.1002/ange.202504499","url":null,"abstract":"Electrocatalytic NO reduction to NH3 holds significant potential for pollutant treatment and resource recovery. Herein, we report that the introduction of CO2 on octahedral oxide-derived copper (o-OD-Cu) significantly enhances the electrochemical reduction of NO to NH3. With 10% NO in a CO2 environment, the Faradaic efficiency for NH3 production in a flow cell remains around 80% over a wide current density range from 20 to 250 mA cm−2. At a current density of 250 mA cm−2, the yield can reach up to 1403.9 µmol cm−2 h−1, which is 3.71 times higher than without CO2 and surpasses the performance reported in similar literature. Moreover, even at a low concentration of 1% NO, the Faradaic efficiency can reach a maximum of 70.11% at a current density of 20 mA cm−2. In situ investigations and theoretical calculations revealed that, in the coexistence of NO and CO2, the NO reduction pathway involves a unique route wherein *CO and *COOH, produced from CO2 reduction, can respectively promote the deoxygenation of *NO and hydrogenation of *N by acquiring O atoms from *NO and providing H atoms for the sustained hydrogenation of *N, thereby accelerating the conversion process of NO to NH3.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Interfacial H-bond Network/Concentration Fields/Electric Fields Regulation Achieved by D-Valine Anions Realizes the Highly Efficient Aqueous Zinc Ion Batteries d -缬氨酸阴离子实现界面氢键网络/浓度场/电场调节实现高效锌离子电池

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202501721

Jiadong Lin, Chenchen Ji, Gaozhi Guo, Yulu Luo, Pengru Huang, Fen Xu, Lixian Sun, Wilhelm Pfleging, Kostya S. Novoselov

{"title":"Interfacial H-bond Network/Concentration Fields/Electric Fields Regulation Achieved by D-Valine Anions Realizes the Highly Efficient Aqueous Zinc Ion Batteries","authors":"Jiadong Lin, Chenchen Ji, Gaozhi Guo, Yulu Luo, Pengru Huang, Fen Xu, Lixian Sun, Wilhelm Pfleging, Kostya S. Novoselov","doi":"10.1002/ange.202501721","DOIUrl":"https://doi.org/10.1002/ange.202501721","url":null,"abstract":"Uncontrolled mobile anions and proton transport result in many issues, including interfacial anion depletion, irregular multiphysics fields fluctuations, space charge layer-induced interfacial Zn dendrites, and hydrogen evolution reaction (HER), which seriously exacerbates the cycling stability of zinc-ion batteries. Herein, this work constructs an efficient D-valine anion interface structure to reversely regulate the Zn2+/H+ dynamic chemistry and unlocks the multiple regulation effects of this anionic interface by investigating interfacial proton transport and complex concentration/electric fields distribution of Zn anode through dynamic in-situ spectroscopy analysis, static energy calculations, and molecular dynamics simulation. We unravel core factors affecting complicated interfacial HER processes and the generation of the space charge layer. This anionic interfacial layer severs proton hopping transport by rupturing the initial water–water hydrogen bond, which effectively restrains uncontrolled HER processes. Further, the anion-immobilized interfacial layer accelerates Zn2+ transfer to optimize the interfacial concentration fields. Also, the anionic interface restrains the formation of the anion depletion layer by relieving rapid Zn2+ ions exhaustion and strengthening the uniformity of interfacial electrical field distribution, which suppresses space charges-induced Zn dendrite growth. Consequently, Zn||Zn symmetric cells deliver an ultralong cycle life of 4150 h. Importantly, the multiple regulation effects enable Zn||I2 cells exhibit long-term stable life.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232325","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nickel-Catalyzed Umpolung Difluoroalkylation of Imines Enables General Access to β-Difluoroalkylated Amines 镍催化亚胺的Umpolung二氟烷基化使一般获得β-二氟烷基化胺

Angewandte Chemie Pub Date : 2025-04-09 DOI: 10.1002/ange.202500990

Fei-Fei Tong, Xiao-Tian Feng, Yuan-Zhan Han, Ming-Chen Huang, Hai-Yang Zhao, Xingang Zhang

引用次数: 0

High-Throughput DFT-Assisted Design of Electrode for Efficient High-Temperature Electrochemical Dehydrogenation 高效高温电化学脱氢电极的高通量dft辅助设计

Angewandte Chemie Pub Date : 2025-04-08 DOI: 10.1002/ange.202502937

Xuepeng Xiang, Zilin Ma, Jun Zhang, Yifeng Li, Yongjian Ye, Wenyu Lu, Mengzhen Zhou, Shasha Huang, Haijun Fu, Bo Yu, Shijun Zhao, Zhang Lin, Yan Chen

{"title":"High-Throughput DFT-Assisted Design of Electrode for Efficient High-Temperature Electrochemical Dehydrogenation","authors":"Xuepeng Xiang, Zilin Ma, Jun Zhang, Yifeng Li, Yongjian Ye, Wenyu Lu, Mengzhen Zhou, Shasha Huang, Haijun Fu, Bo Yu, Shijun Zhao, Zhang Lin, Yan Chen","doi":"10.1002/ange.202502937","DOIUrl":"https://doi.org/10.1002/ange.202502937","url":null,"abstract":"Protonic ceramic electrolysis cell (PCEC) is a promising technique to enable efficient dehydrogenation reactions for producing valuable chemicals, but is still limited by the lack of stable electrocatalysts to achieve efficient O─H/C─H dissociation. In this work, upon high-throughput first-principles calculations, Ba(Zr,Co,Fe,M)O3-based (M represents dopants) perovskite is formulated, and oxygen vacancy formation energy (<math></math>) and hydration energy (ΔEhydr) are taken as two key performance indicators to screen potential PCEC electrode materials derived from this category. Trivalent doping elements, particularly Y, Yb, Er, and Tm, achieve a good balance between <math></math> and ΔEhydr. Experiments further validate that the BaZr0.125Co0.375Fe0.375Tm0.125O3−δ showed impressive dehydrogenation reaction activity, with faradaic efficiency as high as 98.90% in water electrolysis, and outstanding ethane conversion rate (67.60%) and ethylene yield (62.62%) for ethane dehydrogenation reaction at 700 °C. The computational approach can be applied to the rational design of novel electrode materials for other electrochemical reactions in energy and environment devices.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electrostatic Potential Matching in an Anion-Pillared Framework for Benchmark Hexafluoroethane Purification from Ternary Mixture 在阴离子柱框架中静电电位匹配从三元混合物中提纯六氟乙烷

Angewandte Chemie Pub Date : 2025-04-08 DOI: 10.1002/ange.202505355

Shuixiang Zou, Wenjing Zhang, Cheng Chen, Danhua Song, Hengbo Li, Yashuang Li, Jinghong Yang, Rajamani Krishna, Mingyan Wu

{"title":"Electrostatic Potential Matching in an Anion-Pillared Framework for Benchmark Hexafluoroethane Purification from Ternary Mixture","authors":"Shuixiang Zou, Wenjing Zhang, Cheng Chen, Danhua Song, Hengbo Li, Yashuang Li, Jinghong Yang, Rajamani Krishna, Mingyan Wu","doi":"10.1002/ange.202505355","DOIUrl":"https://doi.org/10.1002/ange.202505355","url":null,"abstract":"One-step purification of CF3CF3 from ternary CF3CH2F/CF3CHF2/CF3CF3 mixture is crucial since its vital role in the semiconductor industry. However, efficient separation of chemically inert CF₃CF₃ remains challenging due to the difficulty in creating specific recognition sites in porous materials. In this work, we report the first example of anion-pillared MOFs to the separation of fluorinated electronic specialty gases, utilizing the unique electrostatic potential matching in the bipolar pores of SIFSIX-1-Cu to realize a benchmark CF3CH2F/CF3CHF2/CF3CF3 separation. SIFSIX-1-Cu exhibits the highest CF3CH2F and CF3CHF2 adsorption capacity at 0.01 bar, as well as the highest CF3CH2F/CF3CF3 and CF3CHF2/CF3CF3 IAST selectivity. Additionally, high-purity (≥ 99.995%) CF3CF3 with record productivity (882.9 L kg−1) can be acquired through one-step breakthrough experiment of CF3CH2F/CF3CHF2/CF3CF3 (5/5/90). Theoretical calculations further reveal that the coexistence of electronegative SiF62− and partially electropositive H sites promotes SIFSIX-1-Cu to effectively anchor CF3CH2F and CF3CHF2 through multiple supramolecular interactions.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0