Timur Ashirov, Jay Lim, Alexandra Robles, Thamon Puangsamlee, Patrick W. Fritz, Aurelien Crochet, Xiqu Wang, Connor Hewson, Paul Lacomi, Ognjen Miljanić, Ali Coskun
The recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape-persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np-POP) and the corresponding model compound by reacting cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5-tetraaminobenzene and 1,2-diaminobenzene, respectively, under solvothermal conditions. Co-crystallization of the macrocycle and the model compound with various solvent molecules revealed their size-selective inclusion within the macrocycle. Building on this finding, the np-POP with a hierarchical pore structure and a surface area of 579 m² g−1 showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm—such as acetonitrile and dichloromethane—showed high uptake capacities exceeding 7 mmol g−1. Xylene separation tests revealed a high overall uptake (~34 wt%), with o-xylene displaying a significantly lower uptake (~10 wt% less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents.
{"title":"Porous Organic Polymers Incorporating Shape-persistent Cyclobenzoin Macrocycles for Organic Solvent Separation","authors":"Timur Ashirov, Jay Lim, Alexandra Robles, Thamon Puangsamlee, Patrick W. Fritz, Aurelien Crochet, Xiqu Wang, Connor Hewson, Paul Lacomi, Ognjen Miljanić, Ali Coskun","doi":"10.1002/anie.202423809","DOIUrl":"https://doi.org/10.1002/anie.202423809","url":null,"abstract":"The recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape-persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np-POP) and the corresponding model compound by reacting cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5-tetraaminobenzene and 1,2-diaminobenzene, respectively, under solvothermal conditions. Co-crystallization of the macrocycle and the model compound with various solvent molecules revealed their size-selective inclusion within the macrocycle. Building on this finding, the np-POP with a hierarchical pore structure and a surface area of 579 m² g−1 showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm—such as acetonitrile and dichloromethane—showed high uptake capacities exceeding 7 mmol g−1. Xylene separation tests revealed a high overall uptake (~34 wt%), with o-xylene displaying a significantly lower uptake (~10 wt% less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968485","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}
Nengchao Luo, Xueyuan Wang, Xueshang Xin, Lunqiao Xiong, Jianlong Yang, Tieou Wang, Yang Yang, Zhipeng Huang, Junwang Tang, Feng Wang
Hydroxy radical (•OH) is a prestigious oxidant that allows the cleavage of strong chemical bonds of methane but is untamed, leading to over‐oxidation of methane and waste of oxidants, especially at high methane conversion. Here, we managed to buffer •OH in an aqueous solution of photo‐irradiated Fe3+, where •OH almost participates in methane oxidation. Due to the interaction between Fe3+ and SO42−, the electron transfer from OH− to excited‐state Fe3+ for •OH generation is retarded, while excessive •OH is consumed by generated Fe2+ to restore Fe3+. When combined with a Ru/SrTiO3:Rh photocatalyst, the buffered •OH converts methane to C2+ hydrocarbons and H2 with formation rates of 246 and 418 μmol h−1, respectively. The apparent quantum efficiency reaches 13.0 ± 0.2%, along with 10.2% methane conversion and 81% C2+ selectivity after 80 hours of reaction. Overall, this work presents a strategy for controlling active radicals for selective and efficient photocatalysis.
{"title":"Buffered Hydroxyl Radical for Photocatalytic Non‐Oxidative Methane Coupling","authors":"Nengchao Luo, Xueyuan Wang, Xueshang Xin, Lunqiao Xiong, Jianlong Yang, Tieou Wang, Yang Yang, Zhipeng Huang, Junwang Tang, Feng Wang","doi":"10.1002/anie.202420606","DOIUrl":"https://doi.org/10.1002/anie.202420606","url":null,"abstract":"Hydroxy radical (•OH) is a prestigious oxidant that allows the cleavage of strong chemical bonds of methane but is untamed, leading to over‐oxidation of methane and waste of oxidants, especially at high methane conversion. Here, we managed to buffer •OH in an aqueous solution of photo‐irradiated Fe3+, where •OH almost participates in methane oxidation. Due to the interaction between Fe3+ and SO42−, the electron transfer from OH− to excited‐state Fe3+ for •OH generation is retarded, while excessive •OH is consumed by generated Fe2+ to restore Fe3+. When combined with a Ru/SrTiO3:Rh photocatalyst, the buffered •OH converts methane to C2+ hydrocarbons and H2 with formation rates of 246 and 418 μmol h−1, respectively. The apparent quantum efficiency reaches 13.0 ± 0.2%, along with 10.2% methane conversion and 81% C2+ selectivity after 80 hours of reaction. Overall, this work presents a strategy for controlling active radicals for selective and efficient photocatalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968183","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}
Jiawei Li, Miaojin Wei, Bifa Ji, Sunpei Hu, Jing Xue, Donghao Zhao, Haoyuan Wang, Chunxiao Liu, Yifan Ye, Jilong Xu, Jie Zeng, Ruquan Ye, Yongping Zheng, Tingting Zheng, Chuan Xia
The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity-activity dilemma. In this study, we developed a single-atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60% with a partial current density of -482.7 mA cm-2. Mechanistic investigations revealed that the incorporation of single Co atoms enhances the activation and dissociation of H2O molecules, thereby lowering the energy barrier for the hydrogenation of *CO intermediates. In situ spectroscopic experiments and density functional theory simulations further demonstrated that the modulation of the *CO adsorption configuration, with stronger bridge-binding, favours deep reduction to CH4 over the C-C coupling or CO desorption pathways. Our findings underscore the potential of Co1Cu catalysts in overcoming the selectivity-activity trade-off, paving the way for efficient and scalable CO2-to-CH4 conversion technologies.
{"title":"Copper-Catalysed Electrochemical CO2 Methanation via the Alloying of Single Cobalt Atoms","authors":"Jiawei Li, Miaojin Wei, Bifa Ji, Sunpei Hu, Jing Xue, Donghao Zhao, Haoyuan Wang, Chunxiao Liu, Yifan Ye, Jilong Xu, Jie Zeng, Ruquan Ye, Yongping Zheng, Tingting Zheng, Chuan Xia","doi":"10.1002/anie.202417008","DOIUrl":"https://doi.org/10.1002/anie.202417008","url":null,"abstract":"The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity-activity dilemma. In this study, we developed a single-atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60% with a partial current density of -482.7 mA cm-2. Mechanistic investigations revealed that the incorporation of single Co atoms enhances the activation and dissociation of H2O molecules, thereby lowering the energy barrier for the hydrogenation of *CO intermediates. In situ spectroscopic experiments and density functional theory simulations further demonstrated that the modulation of the *CO adsorption configuration, with stronger bridge-binding, favours deep reduction to CH4 over the C-C coupling or CO desorption pathways. Our findings underscore the potential of Co1Cu catalysts in overcoming the selectivity-activity trade-off, paving the way for efficient and scalable CO2-to-CH4 conversion technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975062","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 reductive deuteration of nitriles is a promising strategy for synthesizing deuterated amines with D2O as the deuterated source. However, this reaction suffers from high overpotentials owing to the sluggish D2O dissociation kinetics and high thermodynamic stability of the C≡N triple bond. Here, low-coordinated copper (LC-Cu) is designed to decrease the overpotential for the electrosynthesis of the precursor of Melatonin-d4, 5-methoxytryptamine-d4, by 100 mV with a 68% yield (Faraday efficiency), which is 4 times greater than that of high-coordinated copper (HC-Cu). The low coordinated sites induced an enrichment of electrons to concentrate K+ ions hydrated deuterium water (K·D2O) and decrease the energy of the Volmer step via the polarization effect, leading to a continuous supplementation of *D for the reductive deuteration of nitriles. Moreover, the enhanced local electric field changes the adsorption configuration of nitriles from a semibridge model to a flat model, leading to faster reduction kinetics of nitriles with a high reaction rate at lower potentials. High deuterium incorporation, a wide substrate scope, and easy gram-scale synthesis over LC-Cu at 300 mA rationalize the design concept. Furthermore, the enhanced antitumor and antioxidation effects of Melatonin-d4 highlight the great promise of deuterated drugs.
{"title":"Defect-Induced Electron Localization Promotes D2O Dissociation and Nitrile Adsorption for Deuterated Amines","authors":"Rui Li, Meng He, Chuanqi Cheng, Fanpeng Chen, Lijun Yang, Jian-Zhong Cui, Cuibo Liu, Bin Zhang","doi":"10.1002/anie.202424039","DOIUrl":"https://doi.org/10.1002/anie.202424039","url":null,"abstract":"Electrochemical reductive deuteration of nitriles is a promising strategy for synthesizing deuterated amines with D2O as the deuterated source. However, this reaction suffers from high overpotentials owing to the sluggish D2O dissociation kinetics and high thermodynamic stability of the C≡N triple bond. Here, low-coordinated copper (LC-Cu) is designed to decrease the overpotential for the electrosynthesis of the precursor of Melatonin-d4, 5-methoxytryptamine-d4, by 100 mV with a 68% yield (Faraday efficiency), which is 4 times greater than that of high-coordinated copper (HC-Cu). The low coordinated sites induced an enrichment of electrons to concentrate K+ ions hydrated deuterium water (K·D2O) and decrease the energy of the Volmer step via the polarization effect, leading to a continuous supplementation of *D for the reductive deuteration of nitriles. Moreover, the enhanced local electric field changes the adsorption configuration of nitriles from a semibridge model to a flat model, leading to faster reduction kinetics of nitriles with a high reaction rate at lower potentials. High deuterium incorporation, a wide substrate scope, and easy gram-scale synthesis over LC-Cu at 300 mA rationalize the design concept. Furthermore, the enhanced antitumor and antioxidation effects of Melatonin-d4 highlight the great promise of deuterated drugs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975059","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}
Aishwarya Prakash, Suma Basappa, Rajashri R. Urkude, Ravindra Jangir, Rajendra S. Dhayal, Shubhankar Kumar Bose
The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance. In addition, a wide range of terminal and challenging internal alkynes were efficiently converted into hydroborated products in up to >99% yield with excellent regioselectivity in the absence of carbon electrophiles. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) analysis confirm that the oxidation state of the copper in the catalyst is zero. The broad range of organic transformations, effectiveness, and recyclability of this Cu0 catalyst are the major achievements that provide an environmentally friendly route for the efficient production of tri- and tetrasubstituted olefins, key intermediates in organic synthesis. The gram-scale reaction and synthetic transformations further highlights the usefulness of these methods.
{"title":"Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes","authors":"Aishwarya Prakash, Suma Basappa, Rajashri R. Urkude, Ravindra Jangir, Rajendra S. Dhayal, Shubhankar Kumar Bose","doi":"10.1002/anie.202418901","DOIUrl":"https://doi.org/10.1002/anie.202418901","url":null,"abstract":"The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance. In addition, a wide range of terminal and challenging internal alkynes were efficiently converted into hydroborated products in up to >99% yield with excellent regioselectivity in the absence of carbon electrophiles. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) analysis confirm that the oxidation state of the copper in the catalyst is zero. The broad range of organic transformations, effectiveness, and recyclability of this Cu0 catalyst are the major achievements that provide an environmentally friendly route for the efficient production of tri- and tetrasubstituted olefins, key intermediates in organic synthesis. The gram-scale reaction and synthetic transformations further highlights the usefulness of these methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975098","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}
Nicholas James Long, Francesco Vanin, William D. J. Tremlett, Danpeng Gao, Qi Liu, Bo Li, Shuai Li, Jianqiu Gong, Xin Wu, Zhen Li, Ryan K. Brown, Liangchen Qian, Chunlei Zhang, Xianglang Sun, Xintong Li, Xiao Cheng Zeng, Zonglong Zhu
Achieving rational control over chemical and energetic properties at the perovskite/electron transport layer (ETL) interface is crucial for realizing highly efficient and stable next-generation inverted perovskite solar cells (PSCs). To address this, we developed multifunctional ferrocene (Fc)-based interlayers engineered to exhibit adjustable passivating and electrochemical characteristics. These interlayers are designed to minimize non-radiative recombination and, to modulate the work function (WF) and uniformity of the perovskite surface, thereby enhancing device performance. The key role played by the highest occupied molecular orbital energies (EHOMO) of the Fc compounds relative to the perovskite valance band maximum (EVBM) is revealed. This relationship is pivotal in controlling band bending and optimizing charge extraction. Notably, the conformationally flexible and more easily oxidized ferrocenyl-bis-furyl-2-carboxylate (2) is found to more effectively bind with undercoordinated Pb2+ surface sites and modulate interfacial energetics, resulting in inverted PSCs achieving champion efficiencies of 25.16%. These cells also displayed excellent stability, retaining >92% of the initial efficiency after 1,000 h of maximum power point operation at 65 °C. By correlating the broadly tunable Fc-EHOMO with a decreased and homogenized perovskite surface WF, our work advances our understanding of Fc-based interlayers and opens new pathways for their application in high-efficiency solar technologies.
{"title":"Modulating Perovskite Surface Energetics Through Tuneable Ferrocene Interlayers for High-Performance Perovskite Solar Cells","authors":"Nicholas James Long, Francesco Vanin, William D. J. Tremlett, Danpeng Gao, Qi Liu, Bo Li, Shuai Li, Jianqiu Gong, Xin Wu, Zhen Li, Ryan K. Brown, Liangchen Qian, Chunlei Zhang, Xianglang Sun, Xintong Li, Xiao Cheng Zeng, Zonglong Zhu","doi":"10.1002/anie.202424041","DOIUrl":"https://doi.org/10.1002/anie.202424041","url":null,"abstract":"Achieving rational control over chemical and energetic properties at the perovskite/electron transport layer (ETL) interface is crucial for realizing highly efficient and stable next-generation inverted perovskite solar cells (PSCs). To address this, we developed multifunctional ferrocene (Fc)-based interlayers engineered to exhibit adjustable passivating and electrochemical characteristics. These interlayers are designed to minimize non-radiative recombination and, to modulate the work function (WF) and uniformity of the perovskite surface, thereby enhancing device performance. The key role played by the highest occupied molecular orbital energies (EHOMO) of the Fc compounds relative to the perovskite valance band maximum (EVBM) is revealed. This relationship is pivotal in controlling band bending and optimizing charge extraction. Notably, the conformationally flexible and more easily oxidized ferrocenyl-bis-furyl-2-carboxylate (2) is found to more effectively bind with undercoordinated Pb2+ surface sites and modulate interfacial energetics, resulting in inverted PSCs achieving champion efficiencies of 25.16%. These cells also displayed excellent stability, retaining >92% of the initial efficiency after 1,000 h of maximum power point operation at 65 °C. By correlating the broadly tunable Fc-EHOMO with a decreased and homogenized perovskite surface WF, our work advances our understanding of Fc-based interlayers and opens new pathways for their application in high-efficiency solar technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"51 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968489","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}
Junjie Wang, Wu Tang, Zhaozhao Zhu, Yingxi Lin, Lei Zhao, Haiyuan Chen, Xueqiang Qi, Xiaobin Niu, Rui Wu, Jun Song Chen
Bismuth oxide (Bi2O3) emerges as a potent catalyst for converting CO2 to formic acid (HCOOH), leveraging its abundant lattice oxygen and the high activity of its Bi-O bonds. Yet, its durability is usually impeded by the loss of lattice oxygen causing structure alteration and destabilized active bonds. Herein, we report an innovative approach via the interstitial incorporation of indium (In) into the Bi2O3, significantly enhancing bond stability and preserving lattice oxygen. The optimized In-Bi2O3-100 catalyst achieves over 90% Faradaic efficiency for HCOOH production across a wide potential range, in both H-cells and flow cells, maintaining robust stability after 100 hours of continuous operation. In-situ surface-enhanced infrared absorption spectroscopy and theoretical calculations reveal that the interstitial In doping precisely tunes the adsorption of CO2* and OCHO* intermediate, facilitating rapid conversion. Further in-situ Raman spectroscopy confirms the role of In bolstering the oxidized structure's stability within Bi2O3, critical for sustaining lattice oxygen during electrochemical CO2 reduction.
{"title":"Stabilizing Lattice Oxygen of Bi2O3 by Interstitial Insertion of Indium for Efficient Formic Acid Electrosynthesis","authors":"Junjie Wang, Wu Tang, Zhaozhao Zhu, Yingxi Lin, Lei Zhao, Haiyuan Chen, Xueqiang Qi, Xiaobin Niu, Rui Wu, Jun Song Chen","doi":"10.1002/anie.202423658","DOIUrl":"https://doi.org/10.1002/anie.202423658","url":null,"abstract":"Bismuth oxide (Bi2O3) emerges as a potent catalyst for converting CO2 to formic acid (HCOOH), leveraging its abundant lattice oxygen and the high activity of its Bi-O bonds. Yet, its durability is usually impeded by the loss of lattice oxygen causing structure alteration and destabilized active bonds. Herein, we report an innovative approach via the interstitial incorporation of indium (In) into the Bi2O3, significantly enhancing bond stability and preserving lattice oxygen. The optimized In-Bi2O3-100 catalyst achieves over 90% Faradaic efficiency for HCOOH production across a wide potential range, in both H-cells and flow cells, maintaining robust stability after 100 hours of continuous operation. In-situ surface-enhanced infrared absorption spectroscopy and theoretical calculations reveal that the interstitial In doping precisely tunes the adsorption of CO2* and OCHO* intermediate, facilitating rapid conversion. Further in-situ Raman spectroscopy confirms the role of In bolstering the oxidized structure's stability within Bi2O3, critical for sustaining lattice oxygen during electrochemical CO2 reduction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968516","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}
Krzystztof Bartkowski, Emran Masoumifeshani, Martyna Kotowska, Urszula Klimczak, Bartłomiej Furman, Cina Foroutan-Nejad, Marcin Lindner
The development of straightforward synthetic methods for photoactive polycyclic aromatic hydrocarbons (PAHs) that avoid Pd-catalyzed or radical-based processes remains a challenge. Such methods are essential to reducing the cost and environmental impact of organic photodevices. In this work, we present a one-pot synthetic approach for creating novel bipolar PAHs with extended π-conjugation, which are not accessible via conventional Pd-catalyzed routes. Our cascade process operates exclusively under basic conditions, utilizing cesium carbonate and molecular sieves to facilitate the coupling of electron-deficient 4-fluoronaphthalene-1,8-dicarboximide with halogenated electron-rich moieties. This results in the regio- and chemoselective formation of new 6- and/or 5-membered conjugated rings via consecutive SNAr reactions, as confirmed through experimental and computational studies. The resulting PAHs exhibit strong emissive properties, with quantum yields ranging from 34% to 99%. This work provides a simple and efficient synthetic strategy for producing novel semiconducting materials, offering a new framework for designing bipolar PAHs with distinct optical characteristics.
{"title":"One-Pot Transition-Metal-Free Synthesis of π-Extended Bipolar Polyaromatic Hydrocarbons","authors":"Krzystztof Bartkowski, Emran Masoumifeshani, Martyna Kotowska, Urszula Klimczak, Bartłomiej Furman, Cina Foroutan-Nejad, Marcin Lindner","doi":"10.1002/anie.202423282","DOIUrl":"https://doi.org/10.1002/anie.202423282","url":null,"abstract":"The development of straightforward synthetic methods for photoactive polycyclic aromatic hydrocarbons (PAHs) that avoid Pd-catalyzed or radical-based processes remains a challenge. Such methods are essential to reducing the cost and environmental impact of organic photodevices. In this work, we present a one-pot synthetic approach for creating novel bipolar PAHs with extended π-conjugation, which are not accessible via conventional Pd-catalyzed routes. Our cascade process operates exclusively under basic conditions, utilizing cesium carbonate and molecular sieves to facilitate the coupling of electron-deficient 4-fluoronaphthalene-1,8-dicarboximide with halogenated electron-rich moieties. This results in the regio- and chemoselective formation of new 6- and/or 5-membered conjugated rings via consecutive SNAr reactions, as confirmed through experimental and computational studies. The resulting PAHs exhibit strong emissive properties, with quantum yields ranging from 34% to 99%. This work provides a simple and efficient synthetic strategy for producing novel semiconducting materials, offering a new framework for designing bipolar PAHs with distinct optical characteristics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968617","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}
In this study, we developed new chiral hybrid perovskites, (R/S‐MBA)(GA)PbI4, by incorporating achiral guanidinium (GA+) and chiral R/S‐methylbenzylammonium (R/S‐MBA+) into the perovskite framework. The resulting materials possess a distinctive structural configuration, positioned between 1D and 2D perovskites, which we describe as 1.5D. This structure is featured by a hydrogen‐bonding‐network‐induced arrangement of zigzag inorganic chains, further forming an organized layered architecture. The structural dimensionality affects both electronic and spin‐related properties. Density functional theory (DFT) calculations reveal Rashba splitting induced by the inversion asymmetry of the crystal structure, while circularly polarized transient absorption spectroscopy confirms spin lifetime on the nanosecond timescale. Magnetic conductive‐probe atomic force microscopy (mCP‐AFM) measurements demonstrate exceptional chiral‐induced spin selectivity (CISS) with maximum spin polarization degrees of (92 ± 1)% and (‐94 ± 2)% for (R‐MBA)(GA)PbI4 and (S‐MBA)(GA)PbI4, respectively. These findings underscore the potential of (R/S‐MBA)(GA)PbI4 as promising candidates for next‐generation spintronic devices, also highlight the critical role of chemical environment in sculpturing the structural dimension and spin‐polarized property of chiral perovskites.
{"title":"1.5D Chiral Perovskites Mediated by Hydrogen‐Bonding Network with Remarkable Spin‐Polarized Property","authors":"Shuo Sun, Jiawei Jiang, Menghui Jia, Yunfei Tian, Yin Xiao","doi":"10.1002/anie.202423314","DOIUrl":"https://doi.org/10.1002/anie.202423314","url":null,"abstract":"In this study, we developed new chiral hybrid perovskites, (R/S‐MBA)(GA)PbI4, by incorporating achiral guanidinium (GA+) and chiral R/S‐methylbenzylammonium (R/S‐MBA+) into the perovskite framework. The resulting materials possess a distinctive structural configuration, positioned between 1D and 2D perovskites, which we describe as 1.5D. This structure is featured by a hydrogen‐bonding‐network‐induced arrangement of zigzag inorganic chains, further forming an organized layered architecture. The structural dimensionality affects both electronic and spin‐related properties. Density functional theory (DFT) calculations reveal Rashba splitting induced by the inversion asymmetry of the crystal structure, while circularly polarized transient absorption spectroscopy confirms spin lifetime on the nanosecond timescale. Magnetic conductive‐probe atomic force microscopy (mCP‐AFM) measurements demonstrate exceptional chiral‐induced spin selectivity (CISS) with maximum spin polarization degrees of (92 ± 1)% and (‐94 ± 2)% for (R‐MBA)(GA)PbI4 and (S‐MBA)(GA)PbI4, respectively. These findings underscore the potential of (R/S‐MBA)(GA)PbI4 as promising candidates for next‐generation spintronic devices, also highlight the critical role of chemical environment in sculpturing the structural dimension and spin‐polarized property of chiral perovskites.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968200","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}
Bohdan Kozibroda, Jean-Marie Lehn, Andrey S Klymchenko
Molecular recognition and detection of small bioactive molecules, like neurotransmitters, remain a challenge for chemists, whereas nature found an elegant solution in form of protein receptors. Here, we introduce a concept of a dynamic artificial receptor that synergically combines molecular recognition with dynamic imine bond formation inside a lipid nanoreactor, inducing a fluorescence response. The designed supramolecular system combines a lipophilic recognition ligand derived from a boronic acid, a fluorescent aldehyde based on push-pull styryl pyridine and a phenol-based catalyst. The recognition ligand specifically captures dopamine inside lipid nanodroplets and thus triggers imine bond formation with the aldehyde, producing the emission color change. The rational design of the fluorescent aldehyde, the catalyst and the recognition ligand allows dramatic acceleration of the imine bond formation required for rapid sensing of dopamine. The nanoprobe enables dopamine detection with micromolar sensitivity and singe-nanoprobe imaging of dopamine gradients through its robust two-color ratiometric response. It displays remarkable selectivity without interference of competing biogenic primary amines and biological media: blood serum, plasma, urine and cell lysate. The proposed concept of a dynamic artificial receptor offers a solution to the long-standing problem of molecular recognition and sensing of small molecules in complex biological media.
{"title":"Fluorescent Artificial Receptor for Dopamine based on Molecular Recognition-driven Dynamic Covalent Chemistry in a Lipid Nanoreactor","authors":"Bohdan Kozibroda, Jean-Marie Lehn, Andrey S Klymchenko","doi":"10.1002/anie.202419905","DOIUrl":"https://doi.org/10.1002/anie.202419905","url":null,"abstract":"Molecular recognition and detection of small bioactive molecules, like neurotransmitters, remain a challenge for chemists, whereas nature found an elegant solution in form of protein receptors. Here, we introduce a concept of a dynamic artificial receptor that synergically combines molecular recognition with dynamic imine bond formation inside a lipid nanoreactor, inducing a fluorescence response. The designed supramolecular system combines a lipophilic recognition ligand derived from a boronic acid, a fluorescent aldehyde based on push-pull styryl pyridine and a phenol-based catalyst. The recognition ligand specifically captures dopamine inside lipid nanodroplets and thus triggers imine bond formation with the aldehyde, producing the emission color change. The rational design of the fluorescent aldehyde, the catalyst and the recognition ligand allows dramatic acceleration of the imine bond formation required for rapid sensing of dopamine. The nanoprobe enables dopamine detection with micromolar sensitivity and singe-nanoprobe imaging of dopamine gradients through its robust two-color ratiometric response. It displays remarkable selectivity without interference of competing biogenic primary amines and biological media: blood serum, plasma, urine and cell lysate. The proposed concept of a dynamic artificial receptor offers a solution to the long-standing problem of molecular recognition and sensing of small molecules in complex biological media.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974937","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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