Xinyu Guo, Chang Li, Yi Zhou, Yan Chen, Wenjun Deng, Rui Li
The application of aqueous zinc-ion batteries (AZIBs) with Zn metal anode is hindered by severe dendritic growth, corrosion, and inefficient Zn utilization. "Rocking-chair" type AZIBs are considered a viable approach toward practical applications due to the success of commercial lithium-ion batteries employing intercalated graphite anodes. Herein, a new type of layered titanium phosphate Ti2O3(H2PO4)2·2H2O is proposed for the first time as the intercalated anodes for AZIBs, exhibiting a capacity of 108 mAh g-1 at 50 mA g-1, with a low discharge potential of 0.17 V (vs. Zn2+/Zn). The ion insertion process was thoroughly investigated, and a micro-dendrite growth-corrosion mode was proposed to explain the capacity degradation mechanism. Corresponding countermeasures were designed, resulting in a significant improvement in cycle life. When coupled with zinc hexacyanoferrate (KZnHCF) cathode, the "rocking-chair" full battery exhibits an ultralong lifespan of 50000 cycles (111 days) at 2.0 A g-1 with 94% capacity retention. This work presents a novel perspective for the development of practical AZIBs.
{"title":"Ti2O3(H2PO4)2·2H2O as a Novel Intercalated Anode for Ultralong Lifespan \"Rocking-chair\" Aqueous Zinc-ion Batteries","authors":"Xinyu Guo, Chang Li, Yi Zhou, Yan Chen, Wenjun Deng, Rui Li","doi":"10.1002/anie.202502446","DOIUrl":"https://doi.org/10.1002/anie.202502446","url":null,"abstract":"The application of aqueous zinc-ion batteries (AZIBs) with Zn metal anode is hindered by severe dendritic growth, corrosion, and inefficient Zn utilization. \"Rocking-chair\" type AZIBs are considered a viable approach toward practical applications due to the success of commercial lithium-ion batteries employing intercalated graphite anodes. Herein, a new type of layered titanium phosphate Ti2O3(H2PO4)2·2H2O is proposed for the first time as the intercalated anodes for AZIBs, exhibiting a capacity of 108 mAh g-1 at 50 mA g-1, with a low discharge potential of 0.17 V (vs. Zn2+/Zn). The ion insertion process was thoroughly investigated, and a micro-dendrite growth-corrosion mode was proposed to explain the capacity degradation mechanism. Corresponding countermeasures were designed, resulting in a significant improvement in cycle life. When coupled with zinc hexacyanoferrate (KZnHCF) cathode, the \"rocking-chair\" full battery exhibits an ultralong lifespan of 50000 cycles (111 days) at 2.0 A g-1 with 94% capacity retention. This work presents a novel perspective for the development of practical AZIBs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640956","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}
Non-adjacent chiral scaffolds are privileged motifs in bioactive molecules and medicines, which has stimulated chemist's ingenuity in achieving the asymmetric construction of non-contiguous chiral elements directly. Current strategies include bifunctional catalysis, synergistic catalysis, cascade catalysis and others, enabling the production of a wide range of enantiomerically enriched compounds fearturing different combinations of non-adjacent chirality, including mutiple central chirality, central and allenyl axial chirality, and central and biaryl axial chirality. Compared to the patterns of mutiple non-adjacent central chirality, the latter two are less frequently reported. This minireview aims to summarize the key developments in reaction design, mechanistic studies, and synthetic applications, with the goal of stimulating further exploration in this important area of asymmetric catalysis.
{"title":"Catalytic Asymmetric Construction of Non-adjacent Stereoelements","authors":"Chong-Lei Ji, Xi-Zhang Zou, De-Wei Gao","doi":"10.1002/anie.202504224","DOIUrl":"https://doi.org/10.1002/anie.202504224","url":null,"abstract":"Non-adjacent chiral scaffolds are privileged motifs in bioactive molecules and medicines, which has stimulated chemist's ingenuity in achieving the asymmetric construction of non-contiguous chiral elements directly. Current strategies include bifunctional catalysis, synergistic catalysis, cascade catalysis and others, enabling the production of a wide range of enantiomerically enriched compounds fearturing different combinations of non-adjacent chirality, including mutiple central chirality, central and allenyl axial chirality, and central and biaryl axial chirality. Compared to the patterns of mutiple non-adjacent central chirality, the latter two are less frequently reported. This minireview aims to summarize the key developments in reaction design, mechanistic studies, and synthetic applications, with the goal of stimulating further exploration in this important area of asymmetric catalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"55 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635538","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}
Self-sustaining afterglow molecules (SAMs) offer high simplicity, reproducibility, and design flexibility compared to common multi-component systems. To date, only a few SAMs have been reported. However, these studies mainly focus on probe selection and screening, without providing an guidance for constructing SAMs from the bottom up. Herein, we report the molecular design and tuning of boron dipyrromethene derivatives (BDs), with structural engineering to enhance the singlet oxygen (1O2) reactivity and photosensitivity, aiming to construct SAMs for activatable afterglow imaging. The optimized BDI-NPs achieve afterglow luminescence at 780 nm following the precise structural creation of BDI, which serves as the role of afterglow initiator, substrate, and relay unit meantime. The BDI can be further customized into an activatable afterglow probe (BDIS-NPs), capable of simultaneously activated fluorescence and afterglow signals for sensing hydrogen disulfide (H2S). Owing to the elimination of autofluorescence and high activation contrast of the afterglow signal, BDIS-NPs enables early monitoring of lipopolysaccharide (LPS)-induced acute lung injury within 15 min and sensitive visualization of H2S accumulation in the brain of schizophrenia mice with a high signal-to-background ratio (SBR), which is not achievable by fluorescence imaging. This study provides an in-depth understanding and design guidelines for SAMs and activatable afterglow imaging.
{"title":"Molecular Engineering of a Self-Sustaining Modular Afterglow Scaffold for In Vivo Activatable Imaging","authors":"Yuyang Zhang, Weina Xu, Diedie Cheng, Meng Zhao, Jiamin Xiong, Qing Li, Qingqing Miao","doi":"10.1002/anie.202500801","DOIUrl":"https://doi.org/10.1002/anie.202500801","url":null,"abstract":"Self-sustaining afterglow molecules (SAMs) offer high simplicity, reproducibility, and design flexibility compared to common multi-component systems. To date, only a few SAMs have been reported. However, these studies mainly focus on probe selection and screening, without providing an guidance for constructing SAMs from the bottom up. Herein, we report the molecular design and tuning of boron dipyrromethene derivatives (BDs), with structural engineering to enhance the singlet oxygen (1O2) reactivity and photosensitivity, aiming to construct SAMs for activatable afterglow imaging. The optimized BDI-NPs achieve afterglow luminescence at 780 nm following the precise structural creation of BDI, which serves as the role of afterglow initiator, substrate, and relay unit meantime. The BDI can be further customized into an activatable afterglow probe (BDIS-NPs), capable of simultaneously activated fluorescence and afterglow signals for sensing hydrogen disulfide (H2S). Owing to the elimination of autofluorescence and high activation contrast of the afterglow signal, BDIS-NPs enables early monitoring of lipopolysaccharide (LPS)-induced acute lung injury within 15 min and sensitive visualization of H2S accumulation in the brain of schizophrenia mice with a high signal-to-background ratio (SBR), which is not achievable by fluorescence imaging. This study provides an in-depth understanding and design guidelines for SAMs and activatable afterglow imaging.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635433","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}
Sandra Lewash, Vivien McKenney, Christine Wuebben, Janos Ludwig, Racha Hosni, Dirk Radzey, Marieta Toma, Martin Schlee, Eva Bartok, Thomas Zillinger, Alexander Heckel, Gunther Hartmann
Photochemical control of oligonucleotides bears great potential for the spatio-temporal control of therapeutic targets, such as immune sensing receptors. Retinoic acid-inducible gene I (RIG-I) is a cytoplasmic receptor of the innate immune system that triggers antiviral responses upon detection of viral RNA.RIG-I can be specifically activated by short double-stranded (ds) RNA with a blunt 5′ end bearing a triphosphate, mimicking nascent viral transcripts. Tumor cells are specifically sensitive to RIG-I-induced cell death. Here we developed a potent oligonucleotide ligand for spatiotemporally controlled activation of RIG-I by light exposure. Through structural considerations and functional studies we identified a combination of two nucleoside positions in a RIG-I oligonucleotide ligand for which the substitution of both respective 2′-hydroxy groups of the ribose by photolabile protecting groups (2′-photocages) resulted in a complete loss of RIG-I ligand activity, whereas photocaging the individual positions was not sufficient to turn off RIG-I. Light exposure fully restored RIG-I activation by the photocaged RIG-I ligand, enabling light-controlled RIG-I-mediated cell death of human cancer cells which had internalized the photocaged RIG-I ligand prior to light exposure. This novel photoactivatable RIG-I oligonucleotide ligand may be applicable for precise light-controlled induction of tumor cell death in superficial cancer such as melanoma.
{"title":"Immunoengineering of a Photocaged 5´-triphosphate Oligoribonucleotide Ligand for Spatiotemporal Control of RIG-I Activation in Cancer","authors":"Sandra Lewash, Vivien McKenney, Christine Wuebben, Janos Ludwig, Racha Hosni, Dirk Radzey, Marieta Toma, Martin Schlee, Eva Bartok, Thomas Zillinger, Alexander Heckel, Gunther Hartmann","doi":"10.1002/anie.202423321","DOIUrl":"https://doi.org/10.1002/anie.202423321","url":null,"abstract":"Photochemical control of oligonucleotides bears great potential for the spatio-temporal control of therapeutic targets, such as immune sensing receptors. Retinoic acid-inducible gene I (RIG-I) is a cytoplasmic receptor of the innate immune system that triggers antiviral responses upon detection of viral RNA.RIG-I can be specifically activated by short double-stranded (ds) RNA with a blunt 5′ end bearing a triphosphate, mimicking nascent viral transcripts. Tumor cells are specifically sensitive to RIG-I-induced cell death. Here we developed a potent oligonucleotide ligand for spatiotemporally controlled activation of RIG-I by light exposure. Through structural considerations and functional studies we identified a combination of two nucleoside positions in a RIG-I oligonucleotide ligand for which the substitution of both respective 2′-hydroxy groups of the ribose by photolabile protecting groups (2′-photocages) resulted in a complete loss of RIG-I ligand activity, whereas photocaging the individual positions was not sufficient to turn off RIG-I. Light exposure fully restored RIG-I activation by the photocaged RIG-I ligand, enabling light-controlled RIG-I-mediated cell death of human cancer cells which had internalized the photocaged RIG-I ligand prior to light exposure. This novel photoactivatable RIG-I oligonucleotide ligand may be applicable for precise light-controlled induction of tumor cell death in superficial cancer such as melanoma.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The continuously increasing mass activity in formic acid oxidation reaction (FAOR) is the key to achieving the practical application of direct formic acid fuel cells (DFAFCs). Herein, Rh-based dual-metal atomic pairs supported on nitrogen-doped carbon catalysts [DAP-(M, Rh)/CN] with adjacent interatomic Rh-M (M = V, Cr, Mn, Fe, Co, Ni, Cu) have been synthesized by a “host-guest” strategy. We discovered that DAP-(Cr, Rh)/CN shows the highest mass activity of 64.1 A·mg-1, which is 3.8 times higher than that of the single atom Rh catalyst (17.0 A·mg-1) and two orders of magnitude higher than Pd/C (0.58 A·mg-1). Interestingly, the mass activity of DAP-(M, Rh)/CN firstly increases from 11.7 A·mg-1 (Rh-V) to 64.1 A·mg-1 (Rh-Cr) and then decreases to 21.8 A·mg-1 (Rh-Cu), forming a volcano curve of the reaction activity. Density functional theory calculations combined with in-situ Fourier transform infrared spectrometer (FTIR) spectra reveal that formic acid oxidized on a series of DAP-(M, Rh)/CN catalysts through the formate route with the subsidiary M metal atoms binding the HCOO species and the Rh atom accepting the H atoms. The most suitable adsorption strength of HCOO on the Cr sites luckily contributes to two spontaneous elementary steps and thus accelerate the FAOR rates.
{"title":"The Cooperative Effects of the Rh-M Dual-Metal Atomic Pairs in Formic Acid Oxidation","authors":"Runze Ma, Jin Zhang, Jiaxin Gong, Yunxiang Lin, Jialin Zhang, Zheng-Qing Huang, Chun-Ran Chang, Shoujie Liu, Wei Zhu, Yuxin Wang, Ke Zeng, Yu Tao, Jinhua Hu, Zedong Zhang, Xiao Liang, Yunhu Han, Junjie Mao, Zechao Zhuang, Jun Yan, Dingsheng Wang, Yu Xiong","doi":"10.1002/anie.202503095","DOIUrl":"https://doi.org/10.1002/anie.202503095","url":null,"abstract":"The continuously increasing mass activity in formic acid oxidation reaction (FAOR) is the key to achieving the practical application of direct formic acid fuel cells (DFAFCs). Herein, Rh-based dual-metal atomic pairs supported on nitrogen-doped carbon catalysts [DAP-(M, Rh)/CN] with adjacent interatomic Rh-M (M = V, Cr, Mn, Fe, Co, Ni, Cu) have been synthesized by a “host-guest” strategy. We discovered that DAP-(Cr, Rh)/CN shows the highest mass activity of 64.1 A·mg-1, which is 3.8 times higher than that of the single atom Rh catalyst (17.0 A·mg-1) and two orders of magnitude higher than Pd/C (0.58 A·mg-1). Interestingly, the mass activity of DAP-(M, Rh)/CN firstly increases from 11.7 A·mg-1 (Rh-V) to 64.1 A·mg-1 (Rh-Cr) and then decreases to 21.8 A·mg-1 (Rh-Cu), forming a volcano curve of the reaction activity. Density functional theory calculations combined with in-situ Fourier transform infrared spectrometer (FTIR) spectra reveal that formic acid oxidized on a series of DAP-(M, Rh)/CN catalysts through the formate route with the subsidiary M metal atoms binding the HCOO species and the Rh atom accepting the H atoms. The most suitable adsorption strength of HCOO on the Cr sites luckily contributes to two spontaneous elementary steps and thus accelerate the FAOR rates.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635539","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}
Carbon nitride (CN), a well-known photocatalyst, has been extensively utilized in light-driven redox reactions, including NADH regeneration. However, its catalytic efficiency is hindered by rapid charge recombination due to obstructed electron transfer. Herein, we developed a highly porous CN coated with a thin layer of rhodium complex (Rh*-PCN) through a combination of bulk and surface engineering for enhanced NADH regeneration. The bulk-engineered porous network of PCN facilitates oriented electron transfer in Rh*-PCN, while the surface-engineered Rh layer minimizes the electron transfer distance between PCN and the rhodium complex. Rh*-PCN achieves an initial NADH regeneration rate of 16.80 mmol g ⁻ ¹ h ⁻ ¹. Moreover, Rh*-PCN suppresses enzyme deactivation by compartmentalizing the enzyme from the photogenerated holes on PCN and the rhodium complex. When integrated with glutamate dehydrogenase, the Rh*-PCN/enzyme coupled system produces L-glutamic acid.
{"title":"Bulk- and Surface-Engineered Carbon Nitride with Promoted Electron Transfer for NADH Regeneration and Artificial Photosynthesis","authors":"Jiafu Shi, Chen Tao, Zhuo Wang, Yexin Dai, Shaohua Zhang, Jing Li, Yu Chen, Xinyu Mao, Zhongyi Jiang","doi":"10.1002/anie.202424995","DOIUrl":"https://doi.org/10.1002/anie.202424995","url":null,"abstract":"Carbon nitride (CN), a well-known photocatalyst, has been extensively utilized in light-driven redox reactions, including NADH regeneration. However, its catalytic efficiency is hindered by rapid charge recombination due to obstructed electron transfer. Herein, we developed a highly porous CN coated with a thin layer of rhodium complex (Rh*-PCN) through a combination of bulk and surface engineering for enhanced NADH regeneration. The bulk-engineered porous network of PCN facilitates oriented electron transfer in Rh*-PCN, while the surface-engineered Rh layer minimizes the electron transfer distance between PCN and the rhodium complex. Rh*-PCN achieves an initial NADH regeneration rate of 16.80 mmol g ⁻ ¹ h ⁻ ¹. Moreover, Rh*-PCN suppresses enzyme deactivation by compartmentalizing the enzyme from the photogenerated holes on PCN and the rhodium complex. When integrated with glutamate dehydrogenase, the Rh*-PCN/enzyme coupled system produces L-glutamic acid.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635533","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}
Christoph Griesser, Sergio Diaz-Coello, Matteo Olgiati, Wanderson Ferraz do Valle, Toni Moser, Andrea Auer, Elena Pastor, Markus Valtiner, Julia Kunze-Liebhäuser
Tungsten carbide (WC) is a renowned compound catalyst material for electrochemical water splitting, and its high electrocatalytic activity towards the hydrogen evolution reaction (HER) has been repeatedly reported. However, its susceptibility to oxidation raises the fundamental question of the underlying reason for its high activity, especially since passivation and thus potential deactivation can occur not only in air but also during reaction. Hence, the investigation of the surface chemistry under true operating conditions is crucial for a fundamental understanding of the electrocatalytic process. In this work we use electrochemical X-ray photoelectron spectroscopy (EC-XPS) to revisit the surface chemistry of WC powder electrodes in alkaline electrolyte in-situ and under full potential control. Our results show that although the surface is initially covered with oxide, this passive film dissolves in the electrolyte under electrochemical reaction conditions. This clarifies the active surface termination during the HER and highlights the potential of laboratory-based EC-XPS to study applied energy conversion materials.
{"title":"Surface Chemistry of WC Powder Electrocatalysts Probed In situ with NAP-XPS","authors":"Christoph Griesser, Sergio Diaz-Coello, Matteo Olgiati, Wanderson Ferraz do Valle, Toni Moser, Andrea Auer, Elena Pastor, Markus Valtiner, Julia Kunze-Liebhäuser","doi":"10.1002/anie.202500965","DOIUrl":"https://doi.org/10.1002/anie.202500965","url":null,"abstract":"Tungsten carbide (WC) is a renowned compound catalyst material for electrochemical water splitting, and its high electrocatalytic activity towards the hydrogen evolution reaction (HER) has been repeatedly reported. However, its susceptibility to oxidation raises the fundamental question of the underlying reason for its high activity, especially since passivation and thus potential deactivation can occur not only in air but also during reaction. Hence, the investigation of the surface chemistry under true operating conditions is crucial for a fundamental understanding of the electrocatalytic process. In this work we use electrochemical X-ray photoelectron spectroscopy (EC-XPS) to revisit the surface chemistry of WC powder electrodes in alkaline electrolyte in-situ and under full potential control. Our results show that although the surface is initially covered with oxide, this passive film dissolves in the electrolyte under electrochemical reaction conditions. This clarifies the active surface termination during the HER and highlights the potential of laboratory-based EC-XPS to study applied energy conversion materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635530","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}
Jian Yang, Bo-Xuan Yao, Huan-Feng Jiang, Shao-Fei Ni, Pierre H. Dixneuf, Min Zhang
Converting planar six-membered aza-arenes into C(sp3)-rich three-dimensional (3D) scaffolds is a promising way to obtain isosteric mimetics of numerous functional products, but it remains to date a formidable challenge due to the high thermodynamic stability and dynamic inertness as well as the selectivity control. Here, by applying a novel non-noble bimetallic Mn/Fe catalyst system, we report, for the first time, an approach for direct construction of functional 3D 2-azabicyclo[2.1.1]hexanes via a hydrodearomatization (HDA) of the aza-arenes and [2π + 2σ] cycloaddition cascade. Mechanistic investigations reveal that the triplet state of Fe(II) facilitates the activation of both aza-arenes and bicyclo[1.1.0]butanes (BCBs). The mild reduction nature of manganese catalysis and the steric effects of Fe(II) coordination result in an 1,4-hydrodearomatization, and the imine species derived from the isomerization of 1,4-hydrogenated aza-arenes are then effectively trapped by the polarized BCBs, thus suppressing the thermodynamically favorable over-hydrogenation of aza-arenes into cyclic amine by-products. Given the features of good substrate and functionality compatibility, high step and atom efficiency, and diversified product post-transformations, the developed chemistry offers a practical platform to access various functional molecules.
{"title":"Direct Access to Functional 2-Azabicyclo[2.1.1]hexanes via Hydrodearomative [2π + 2σ] Cycloaddition of Aza-arenes","authors":"Jian Yang, Bo-Xuan Yao, Huan-Feng Jiang, Shao-Fei Ni, Pierre H. Dixneuf, Min Zhang","doi":"10.1002/anie.202505060","DOIUrl":"https://doi.org/10.1002/anie.202505060","url":null,"abstract":"Converting planar six-membered aza-arenes into C(sp3)-rich three-dimensional (3D) scaffolds is a promising way to obtain isosteric mimetics of numerous functional products, but it remains to date a formidable challenge due to the high thermodynamic stability and dynamic inertness as well as the selectivity control. Here, by applying a novel non-noble bimetallic Mn/Fe catalyst system, we report, for the first time, an approach for direct construction of functional 3D 2-azabicyclo[2.1.1]hexanes via a hydrodearomatization (HDA) of the aza-arenes and [2π + 2σ] cycloaddition cascade. Mechanistic investigations reveal that the triplet state of Fe(II) facilitates the activation of both aza-arenes and bicyclo[1.1.0]butanes (BCBs). The mild reduction nature of manganese catalysis and the steric effects of Fe(II) coordination result in an 1,4-hydrodearomatization, and the imine species derived from the isomerization of 1,4-hydrogenated aza-arenes are then effectively trapped by the polarized BCBs, thus suppressing the thermodynamically favorable over-hydrogenation of aza-arenes into cyclic amine by-products. Given the features of good substrate and functionality compatibility, high step and atom efficiency, and diversified product post-transformations, the developed chemistry offers a practical platform to access various functional molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635535","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}
We describe how the merger of deprotonation, halogenation and substitution into compatible processes enables the productive functionalization of traditionally unstable carbanionic intermediates. This strategy enables the first oxidative coupling protocol of α,α-difluorobenzylic C–H bonds with heteronucleophiles. Here, transiently generated α,α-difluorobenzylic carbanionic intermediates undergo halogen transfer from 2-bromothiophenes to form electrophilic ArCF2Br compounds for in situ nucleophilic substitution, thereby avoiding α-fluoride elimination pathways that typically plague α-fluorocarbanions. This method streamlines the modular synthesis of α,α-difluorobenzyl(thio)ethers and led to the broader realization that halogen transfer to unstable carbanions is an enabling principle across diverse C(sp2)–H and C(sp3)–H systems.
{"title":"Capturing Unstable Carbanionic Intermediates via Halogen Transfer: Base-Promoted Oxidative Coupling Reactions of α,α-Difluoromethylarenes","authors":"Leidy V. Hooker, Jeffrey S. Bandar","doi":"10.1002/anie.202502894","DOIUrl":"https://doi.org/10.1002/anie.202502894","url":null,"abstract":"We describe how the merger of deprotonation, halogenation and substitution into compatible processes enables the productive functionalization of traditionally unstable carbanionic intermediates. This strategy enables the first oxidative coupling protocol of α,α-difluorobenzylic C–H bonds with heteronucleophiles. Here, transiently generated α,α-difluorobenzylic carbanionic intermediates undergo halogen transfer from 2-bromothiophenes to form electrophilic ArCF2Br compounds for in situ nucleophilic substitution, thereby avoiding α-fluoride elimination pathways that typically plague α-fluorocarbanions. This method streamlines the modular synthesis of α,α-difluorobenzyl(thio)ethers and led to the broader realization that halogen transfer to unstable carbanions is an enabling principle across diverse C(sp2)–H and C(sp3)–H systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640958","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}
Yuxi Guo, Wentao Xie, Zeyuan Ye, Ke Xu, Zhenghao Zhang, Zhengqi Xiao, Jingsheng Miao, Yang Zou, Cheng Zhong, Xiaojun Yin, Chuluo Yang, Xiaosong Cao
High-efficiency, pure deep-blue emitters are critically needed to meet the rising demands of ultrahigh-definition displays. Although high-order B/N-doped polycyclic aromatic hydrocarbons (PAHs) leveraging multi-resonance (MR) effects show promise, their complex syntheses and large molecular weights hinder practical application. Here, we report a compact MR framework featuring three nitrogen-linked boron centers, synthesized at the gram scale via a single-step, amine-directed borylation. This emitter displays deep-blue emission with an ultranarrow full-width at half-maximum (FWHM) of 13 nm and achieves an order-of-magnitude increase in the reverse intersystem crossing rate constant (kRISC) compared to previous BN-bond-based blue MR emitters. Theoretical studies reveal that its π-extended framework and partially distorted geometry synergistically minimize structural relaxation to reduce FWHM and enhance spin–orbit coupling to facilitate efficient spin-flip processes. As a result, the corresponding deep-blue organic light-emitting diodes exhibits a FWHM of 15 nm, and a high maximum external quantum efficiency (ηEQE,max) approaching 30% at color coordinates of (0.155, 0.060), rivaling the leading performance of deep-blue OLEDs based on conventional B/N-doped frameworks.
{"title":"Simple Boron-Nitrogen Covalent Bond Constructs Multi-Resonance TADF Emitters: Ultra-Narrowband Deep-Blue Electroluminescence","authors":"Yuxi Guo, Wentao Xie, Zeyuan Ye, Ke Xu, Zhenghao Zhang, Zhengqi Xiao, Jingsheng Miao, Yang Zou, Cheng Zhong, Xiaojun Yin, Chuluo Yang, Xiaosong Cao","doi":"10.1002/anie.202503320","DOIUrl":"https://doi.org/10.1002/anie.202503320","url":null,"abstract":"High-efficiency, pure deep-blue emitters are critically needed to meet the rising demands of ultrahigh-definition displays. Although high-order B/N-doped polycyclic aromatic hydrocarbons (PAHs) leveraging multi-resonance (MR) effects show promise, their complex syntheses and large molecular weights hinder practical application. Here, we report a compact MR framework featuring three nitrogen-linked boron centers, synthesized at the gram scale via a single-step, amine-directed borylation. This emitter displays deep-blue emission with an ultranarrow full-width at half-maximum (FWHM) of 13 nm and achieves an order-of-magnitude increase in the reverse intersystem crossing rate constant (kRISC) compared to previous BN-bond-based blue MR emitters. Theoretical studies reveal that its π-extended framework and partially distorted geometry synergistically minimize structural relaxation to reduce FWHM and enhance spin–orbit coupling to facilitate efficient spin-flip processes. As a result, the corresponding deep-blue organic light-emitting diodes exhibits a FWHM of 15 nm, and a high maximum external quantum efficiency (ηEQE,max) approaching 30% at color coordinates of (0.155, 0.060), rivaling the leading performance of deep-blue OLEDs based on conventional B/N-doped frameworks.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635468","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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