Angewandte Chemie International Edition最新文献_第8页

Suppressing the Interface Photodegradation Towards Efficient and Stable All Perovskite Tandem Solar Cells 抑制界面光降解以实现高效稳定的全钙钛矿串联太阳能电池

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-24 DOI: 10.1002/anie.202424825

Zhuojia Lin, Jianwei Chen, Kezhou Fan, Jicheng Yi, Honggang Chen, Shibing Zou, Hongyu Min, Yitong Xu, Man Yu Lam, Sergeev A. Aleksandr, Kam Sing Wong, He Yan, Keyou Yan

{"title":"Suppressing the Interface Photodegradation Towards Efficient and Stable All Perovskite Tandem Solar Cells","authors":"Zhuojia Lin, Jianwei Chen, Kezhou Fan, Jicheng Yi, Honggang Chen, Shibing Zou, Hongyu Min, Yitong Xu, Man Yu Lam, Sergeev A. Aleksandr, Kam Sing Wong, He Yan, Keyou Yan","doi":"10.1002/anie.202424825","DOIUrl":"https://doi.org/10.1002/anie.202424825","url":null,"abstract":"All perovskite tandem solar cells (PTSCs) were expected to overcome the Shockley‐Queisser limit of single‐junction perovskite solar cells (PSCs). Nevertheless, wide bandgap (WBG) subcells suffer from large photovoltage losses and device instability due to extensive film defect, interfacial degradation and phase segregation. Herein, a polymeric multi‐dentate anchoring (PMDA) strategy by introducing poly(carbazole phosphonic acid) was employed to engineer the bottom interface and suppress phase segregation. The reinforced and homogeneous anchorage by multiple repeat phosphonic acid groups onto NiOx significantly optimise the bottom interface, suppress unfavourable interfacial reactions and thus alleviate phase segregation of WBG perovskite. As a result, the PMDA‐modified WBG PSCs showed higher power conversion efficiency (PCE) than the control device (19.84% versus 18.18%), along with better device photostability (T80 = 1200 versus 500 hours). Coupled with narrow bandgap (NBG) PSCs, the PMDA‐modified PTSCs reached a PCE of up to 28.51% with device operation photostability over 700 hours (T80).","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"133 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130653","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

Guest Polarizability Directed Molecular 'Freezing' within Non-metal Porous Salt Frameworks. 非金属多孔盐框架内客体极化率定向分子“冻结”。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202509905

Yi Xie,Qiang Gao,Jianchen Wang,Gang Ye,Banglin Chen

{"title":"Guest Polarizability Directed Molecular 'Freezing' within Non-metal Porous Salt Frameworks.","authors":"Yi Xie,Qiang Gao,Jianchen Wang,Gang Ye,Banglin Chen","doi":"10.1002/anie.202509905","DOIUrl":"https://doi.org/10.1002/anie.202509905","url":null,"abstract":"Isoreticular non-metal salt frameworks with permanent porosity have emerged recently as a fantastic platform for molecular separation, but the underlying guest-framework interactions within their charge-separated ionic channels remain to be explored. Here, we report the first case of guest polarizability-directed molecular 'freezing' of noble gas occurring within a non-metal porous organic ammonium framework, which bears well-organized, high-density chloride anions as nodes. Notably, the framework exhibits a distinctive, thermally-independent commensurate adsorption towards highly polarizable Xe, while traditional thermodynamic adsorption behaviors are observed for Kr with lower polarizability. A remarkable Xe adsorption capacity of 1.47 mmol/g and a record-high separation factor of 10.2 are thus achieved in dynamic Xe/Kr separation under ambient conditions. The practical potential for realistic Xe/Kr separation from the off-gas of used nuclear fuel (UNF) reprocessing is demonstrated. Theoretical calculations identify the presence of multiple strong Xe···Cl interactions as the driving force within the size-matching ionic channels of the salt framework.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e202509905"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122203","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

Nucleation and Growth Mechanisms of Micro/Nano Structural Manganese-Trimesic Acid Coordinations for Aqueous Zinc-Ion Batteries. 锌离子电池微纳结构锰-三聚酸配位物的成核和生长机理

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202509741

Qian Li,Yanfei Zhang,Xiaotian Guo,Zhangbin Yang,Yixuan Wang,Yumeng Chen,Yiwen Liu,Haotian Yue,Shengjie Gao,Huijie Zhou,Jianfei Huang,Mohsen Shakouri,Yonggang Wang,Guoyin Zhu,Zheng Liu,Yizhou Zhang,Huan Pang

{"title":"Nucleation and Growth Mechanisms of Micro/Nano Structural Manganese-Trimesic Acid Coordinations for Aqueous Zinc-Ion Batteries.","authors":"Qian Li,Yanfei Zhang,Xiaotian Guo,Zhangbin Yang,Yixuan Wang,Yumeng Chen,Yiwen Liu,Haotian Yue,Shengjie Gao,Huijie Zhou,Jianfei Huang,Mohsen Shakouri,Yonggang Wang,Guoyin Zhu,Zheng Liu,Yizhou Zhang,Huan Pang","doi":"10.1002/anie.202509741","DOIUrl":"https://doi.org/10.1002/anie.202509741","url":null,"abstract":"Nucleation and growth of metal-organic frameworks (MOFs) are critical for controlling their morphology, size, and performance. Guided by the crystal nucleation and growth theory, this study systematically explored the effects of the sequential addition of ligand trimesic acid (BTC) and manganese ions (Mn2+), ligand-to-metal ion ratio, solvent composition, and surfactants on the nucleation and growth of MnBTC. The regulatory mechanisms of the crystal morphology and internal structure were deeply revealed. Moreover, the established machine learning (ML) model can accurately predict the concentrations of -COO- and Mn2+, providing important guidance for the controlled synthesis of MOFs in the future. In practical, the electrochemical performance of MnBTC with different morphologies and sizes was evaluated for aqueous zinc-ion batteries. The reaction mechanism of MnBTC during the charge-discharge process was investigated through a series of in-situ and ex-situ characterizations, and MnBTC demonstrated excellent energy-storage performance. This study opens a new window for the precise synthesis of MOFs which show strongly controlled micro/nano structure and coordination environment based on the crystal nucleation and growth theory with the assistance of ML.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":"e202509741"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122204","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

Universal Metal-Exchange Strategy for Room Temperature Synthesis of Single-Atom Nanozymes. 室温合成单原子纳米酶的通用金属交换策略。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202505123

Zhang Jie,Zezhong Huang,Bolong Xu,Qingyuan Wu,Zhijun Huang,Huiyu Liu

引用次数: 0

Ether-Oxygen Groups Modified Carboxylic Ester Enabling High-Voltage Lithium Metal Batteries. 用于高压锂金属电池的醚氧基改性羧酸酯。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202504490

Shuang Li,Hongliang Xie,Pushpendra Kumar,Yinghua Chen,Jia Wang,Akang Huang,Wandi Wahyudi,Hui Zhu,Jiao Yin,Qian Li,Zheng Ma,Jun Ming

{"title":"Ether-Oxygen Groups Modified Carboxylic Ester Enabling High-Voltage Lithium Metal Batteries.","authors":"Shuang Li,Hongliang Xie,Pushpendra Kumar,Yinghua Chen,Jia Wang,Akang Huang,Wandi Wahyudi,Hui Zhu,Jiao Yin,Qian Li,Zheng Ma,Jun Ming","doi":"10.1002/anie.202504490","DOIUrl":"https://doi.org/10.1002/anie.202504490","url":null,"abstract":"Lithium metal batteries (LMBs) operating at high cut-off voltages can achieve an energy density exceeding 500 Wh kg-1; however, they often suffer from severe capacity degradation due to electrolyte decomposition. Herein, propylene glycol methyl ether acetate (PMA) is introduced as a novel solvent for LMB electrolytes. The unique ether-oxygen functionality in PMA exhibits high steric hindrance, leading to weak lithium-ion coordination, which promotes the formation of contact ion pairs (CIPs) in the electrolyte solvation structure, especially in the presence of dual salts. A Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) battery employing the formulated PMA-based electrolyte demonstrates stable cycling at a high cut-off voltage of 4.5 V for over 100 cycles, retaining 90.1% of its initial capacity even at 60°C. Furthermore, a molecular interfacial model is proposed to elucidate the impact of the designed electrolyte on electrode interfacial behavior and battery performance, providing valuable insights for the development of high-performance LMB electrolytes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":"e202504490"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122325","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

In Situ Solid Conversion into Mechanically Adaptive LiF-Rich Solid Electrolyte Interphase via MgF2 precursor on Si Surface in Lithium-Ion Batteries. 基于硅表面MgF2前驱体的锂离子电池原位固体转化为机械自适应富liff固体电解质界面

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202507688

Jiayang Sun,Linze Lv,Yuchen Li,Yan Wang,Longfei Wang,Weixing Xiong,Lei Huang,Qunting Qu,Honghe Zheng

{"title":"In Situ Solid Conversion into Mechanically Adaptive LiF-Rich Solid Electrolyte Interphase via MgF2 precursor on Si Surface in Lithium-Ion Batteries.","authors":"Jiayang Sun,Linze Lv,Yuchen Li,Yan Wang,Longfei Wang,Weixing Xiong,Lei Huang,Qunting Qu,Honghe Zheng","doi":"10.1002/anie.202507688","DOIUrl":"https://doi.org/10.1002/anie.202507688","url":null,"abstract":"Silicon (Si) anodes hold exceptional promise for high-energy-density lithium-ion batteries (LIBs) due to their ultrahigh theoretical capacity (~4200 mAh g⁻¹). However, their commercialization is severely hindered by the significant volume expansion (~300%) and unstable solid electrolyte interphase (SEI). Conventional SEI, predominantly composed of organic species, suffers from low ionic conductivity, low electronic insulation and poor mechanical robustness, leading to rapid capacity decay. Herein, we propose an interface engineering strategy by decorating Si nanoparticles with an in-situ conversed MgF₂ layer (with coating integrity of 94.6%). During initial lithiation, the applied MgF₂ layer is in-situ conversed into SEI film with high ionic conductivity, electronic insulation and better mechanical adaptability. The prepared Si@MgF₂-1 anode achieves a high initial coulombic efficiency (91.7%), superior rate capability (2000 mAh g⁻¹ at 10 C), and remarkable cycling stability (1794.9 mAh g-1 after 500 cycles). Full-cell based on the Si@MgF₂-1 anode and NCM811 cathode further validate the practicality of this approach. The robust conversion strategy for the construction of a mechanically adaptive LiF-rich SEI layer holds significant promise for the advancement of durable silicon-based LIBs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e202507688"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122206","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

Intermediate Layer-Engineered Lanthanide Nanoparticles Enable Deep Bioorthogonal Liver Tumor and Vascular Imaging via Switchable NIR-II Emissions. 中间层工程镧系纳米颗粒通过可切换的NIR-II发射实现深层生物正交肝脏肿瘤和血管成像。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202507787

Kehong Lv,Hongxia Yue,Chunyan Li,Shengzhe Chen,Hongli Wang,Ruohao Zhang,Jing Feng,Hongjie Zhang

{"title":"Intermediate Layer-Engineered Lanthanide Nanoparticles Enable Deep Bioorthogonal Liver Tumor and Vascular Imaging via Switchable NIR-II Emissions.","authors":"Kehong Lv,Hongxia Yue,Chunyan Li,Shengzhe Chen,Hongli Wang,Ruohao Zhang,Jing Feng,Hongjie Zhang","doi":"10.1002/anie.202507787","DOIUrl":"https://doi.org/10.1002/anie.202507787","url":null,"abstract":"The second near-infrared window (NIR-II) has become an attractive optical region for fluorescence imaging. However, due to the complexity in vivo, NIR-II light with various wavelengths for different imaging sences has not been investigated. Here, we found that 1525 nm light is suitable for high-resolution fluorescence imaging due to low background interference, while its attenuation in vivo makes it unsuitable for deep imaging. The 1064 nm light is suitable for deep imaging. The impact of Yb3+ ions and the proportion of the intermediate layer in lanthanide nanoparticles on the modulation of emissions were investigated. The intense 1064 nm emission is achievable when the Yb3+ content is 80% and the intermediate layer proportion is 0.1. The bioorthogonal orthotopic liver tumor imaging could be achieved by modifying the lanthanide nanoparticles with DBCO-PEG2000-DSPE and establishing artificial receptors by N-azidoacetylmannosamine-tetraacylated (Ac4ManNAz). Lanthanide nanoparticles with the intermediate layer proportion of 0.66 and 80% Yb3+ facilitate intense 1525 nm emission, enabling the vascular imaging. Based on the imaging characteristics of NIR-II emissions with different wavelengths in vivo, this work achieves high-resolution imaging and deep imaging through intermediate layer regulation of lanthanide nanoparticles, providing an opportunity to explore a new generation of high-performance fluorescent probes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":"e202507787"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122202","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

Negatively Curved Diaza-Octagon Heterocycle Fused with Polycyclic Aromatic Hydrocarbons for Ultra-Narrowband Deep-Blue Emission. 负弯曲diaza -八角形杂环与多环芳烃融合的超窄带深蓝色辐射。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202506504

Baoxi Li,Yadong Qu,Jingli Lou,Lu Liu,Yu Huang,Han Zhang,Ben Zhong Tang,Zhiming Wang

{"title":"Negatively Curved Diaza-Octagon Heterocycle Fused with Polycyclic Aromatic Hydrocarbons for Ultra-Narrowband Deep-Blue Emission.","authors":"Baoxi Li,Yadong Qu,Jingli Lou,Lu Liu,Yu Huang,Han Zhang,Ben Zhong Tang,Zhiming Wang","doi":"10.1002/anie.202506504","DOIUrl":"https://doi.org/10.1002/anie.202506504","url":null,"abstract":"Developing new polycyclic aromatic hydrocarbons (PAHs) skeletons with narrowband emission is crucial for advancing ultra-high-definition displays. Inspired by the aesthetic configuration of negatively curved octagonal rings and the multiple resonance (MR) effect, we designed a novel diaza-octagon heterocycle fused with PAHs, abbreviated as 8NN, and its phenyl-substituted derivative 8NNP. Crystal data and theoretical calculations show that their peripheral PAHs exhibit significant rigidity, while the internal diaza-octagon ring confers skeleton flexibility and flipping properties. Notably, owing to the strategic embedding and unique bonding form of nitrogen atoms, their MR effect is significantly enhanced. Finally, 8NN and 8NNP achieve deep-blue emission peaking at 408 nm and 411 nm, with remarkably narrow full-width at half-maximum (FWHM) of 19 nm and 17 nm, respectively, and aggregation-enhanced emission characteristics. Additionally, to further tune emission range of this new skeleton, boron-functionalized 8NNB was synthesized, achieving blue emission peaking at 461 nm in toluene, with a FWHM of 31 nm. Finally, the OLEDs based on 8NNP and 8NNB exhibit maximum external quantum efficiencies of 3.47% and 24.24%, with CIE coordinates of (0.172, 0.043) and (0.132, 0.256), respectively. These results validate the rational design of the novel skeleton and facilitate the development of narrowband emission materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 3 1","pages":"e202506504"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122208","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

Evidence for Methylaluminoxane (MAO) Molecular Structure and Reactivity from Ultra-High Magnetic Field 27Al MAS NMR Spectroscopy Combined with DFT Calculations. 超高磁场27Al MAS NMR结合DFT计算甲基铝氧烷（MAO）分子结构和反应性的证据

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202508409

Kai C Szeto,Mostafa Taoufik,Franck Fayon,David Gajan,Eva Zurek,Jochen Autschbach,Julien Trebosc,Laurent Delevoye,Régis Michaël Gauvin

{"title":"Evidence for Methylaluminoxane (MAO) Molecular Structure and Reactivity from Ultra-High Magnetic Field 27Al MAS NMR Spectroscopy Combined with DFT Calculations.","authors":"Kai C Szeto,Mostafa Taoufik,Franck Fayon,David Gajan,Eva Zurek,Jochen Autschbach,Julien Trebosc,Laurent Delevoye,Régis Michaël Gauvin","doi":"10.1002/anie.202508409","DOIUrl":"https://doi.org/10.1002/anie.202508409","url":null,"abstract":"The structure and reactivity of methylaluminoxane (MAO), a reagent of major interest for olefin polymerization, both industrially and academically, has been probed using ultra-high magnetic field solid-state NMR spectroscopy (28.2 T, 1200 MHz for 1H Larmor frequency). High resolution methods combined with density functional calculations allowed for the identification and quantification of five major aluminum sites, providing precise information on the structure of MAO at the molecular level. Based on reactivity studies with THF and [ZrCp2Me2], the main reactive centers are identified as bismethyl aluminum species stabilized via a bridging methyl group from a neighboring Al center, featuring both high chemical shift and quadrupolar coupling constants (162 ppm and 27.4 MHz, respectively). The ultra-high magnetic field NMR spectroscopy and DFT calculations combined approach demonstrates the ability to monitor the chemistry of MAO with unprecedented precision, enabling a state-of-the-art understanding of its structure and reactivity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":"e202508409"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122254","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

Multiply Substituted (Hetero)acenes with a Phosphonate Group at the Central Unit as High-Efficiency Light Emitters. 在中心单元与膦酸基团相乘取代（杂）烯作为高效发光体。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-23 DOI: 10.1002/anie.202508168

Marek Koprowski,Łucja Knopik,Ewa Różycka-Sokołowska,Bogdan Dudziński,Vivek Vivek,Krzysztof Owsianik,Piotr Bałczewski

{"title":"Multiply Substituted (Hetero)acenes with a Phosphonate Group at the Central Unit as High-Efficiency Light Emitters.","authors":"Marek Koprowski,Łucja Knopik,Ewa Różycka-Sokołowska,Bogdan Dudziński,Vivek Vivek,Krzysztof Owsianik,Piotr Bałczewski","doi":"10.1002/anie.202508168","DOIUrl":"https://doi.org/10.1002/anie.202508168","url":null,"abstract":"A new variant of the Friedel-Crafts-Bradsher reaction offers access to dialkoxyphosphoryl substituted (hetero)acenes, especially to previously unavailable three- to seven-substituted, tri- and tetracyclic compounds, and features high chemical yields up to 95%, excellent photoluminescence quantum yields (QY) up to 87.7%, large Stokes shifts up to 7943 cm-1 and very mild, room temperature reaction conditions. The (RO)2P(O) has a distinct effect on the photophysical properties of acenes, increasing QYs by more than twofold compared to identical acenes, not substituted by this group. DFT and TD-DFT calculations, combined with electron-hole analysis, indicated that local excitation (LE) had the dominant contribution to the electron excitation mechanism, and charge transfer (CT) of about 30% provided the highest fluorescence quantum yields. Multiply substitution of (hetero)acenes bearing phosphonate moiety and electron-diverse substituents combined with a lower number of fused aromatic rings, appear to be ideal for optimal chemical stability and high photoluminescence. The new, synthetic tool will accelerate exploitation of bulky (hetero)acene emitters for optoelectronic applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"169 1","pages":"e202508168"},"PeriodicalIF":16.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122328","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