Alkali metals (e.g. Li, Na, and K) and multivalent metals (e.g. Zn, Mg, Ca, and Al) have become star anodes for developing high-energy-density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid-state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.
{"title":"Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly-Efficient Rechargeable Batteries.","authors":"Jianlu Sun, Fangyuan Kang, Dongbo Yan, Tangjing Ding, Yulong Wang, Xiaosi Zhou, Qichun Zhang","doi":"10.1002/anie.202406511","DOIUrl":"10.1002/anie.202406511","url":null,"abstract":"<p><p>Alkali metals (e.g. Li, Na, and K) and multivalent metals (e.g. Zn, Mg, Ca, and Al) have become star anodes for developing high-energy-density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid-state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140846939","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}
Catalytic removal of alkynes is essential in industry for producing polymer-grade alkenes from steam cracking processes. Non-noble Ni-based catalysts hold promise as effective alternatives to industrial Pd-based catalysts but suffer from low activity. Here we report embedding of single-atom Pd onto the NiGa intermetallic surface with replacing Ga atoms via a well-defined synthesis strategy to design Pd1-NiGa catalyst for alkyne semi-hydrogenation. The fabricated Pd1Ni2Ga1 ensemble sites deliver remarkably higher specific mass activity under superb alkene selectivity of >96% than the state-of-the-art catalysts under industry-relevant conditions. Integrated experimental and computational studies reveal that the single-atom Pd located synergizes with the neighbouring Ni sites to facilitate the σ-adsorption of alkyne and dissociation of hydrogen while suppress the alkene adsorption. Such synergistic effects confer the single-atom Pd on the NiGa intermetallic with a Midas touch for alkyne semi-hydrogenation, providing an effective strategy for stimulating low active Ni-based catalysts for other selective hydrogenations in industry.
催化脱除炔烃在工业中对于从蒸汽裂解工艺中生产聚合物级烯烃至关重要。非贵金属镍基催化剂有望成为工业钯基催化剂的有效替代品,但活性较低。在此,我们报告了通过一种定义明确的合成策略将单原子钯嵌入 NiGa 金属间表面并取代 Ga 原子,从而设计出用于炔烃半加氢的 Pd1-NiGa 催化剂。在工业相关条件下,制备的 Pd1Ni2Ga1 组合位点的烯选择性大于 96%,比最先进的催化剂具有更高的比质量活性。综合实验和计算研究表明,单原子钯位点与邻近的镍位点协同作用,促进了炔的σ吸附和氢的解离,同时抑制了烯的吸附。这种协同效应使 NiGa 金属间化合物上的单原子 Pd 在炔烃半加氢反应中发挥了 Midas touch 的作用,为工业中其他选择性加氢反应的低活性 Ni 基催化剂提供了有效的激励策略。
{"title":"Embedding Single Pd Atoms on NiGa Intermetallic Surfaces for Efficient and Selective Alkyne Semi-hydrogenation.","authors":"Xiaohu Ge, Yundao Jing, Nina Fei, Kelin Yan, Yijing Liang, Yueqiang Cao, Jing Zhang, Gang Qian, Lina Li, Hao Jiang, Xinggui Zhou, Weikang Yuan, Xuezhi Duan","doi":"10.1002/anie.202410979","DOIUrl":"https://doi.org/10.1002/anie.202410979","url":null,"abstract":"<p><p>Catalytic removal of alkynes is essential in industry for producing polymer-grade alkenes from steam cracking processes. Non-noble Ni-based catalysts hold promise as effective alternatives to industrial Pd-based catalysts but suffer from low activity. Here we report embedding of single-atom Pd onto the NiGa intermetallic surface with replacing Ga atoms via a well-defined synthesis strategy to design Pd1-NiGa catalyst for alkyne semi-hydrogenation. The fabricated Pd1Ni2Ga1 ensemble sites deliver remarkably higher specific mass activity under superb alkene selectivity of >96% than the state-of-the-art catalysts under industry-relevant conditions. Integrated experimental and computational studies reveal that the single-atom Pd located synergizes with the neighbouring Ni sites to facilitate the σ-adsorption of alkyne and dissociation of hydrogen while suppress the alkene adsorption. Such synergistic effects confer the single-atom Pd on the NiGa intermetallic with a Midas touch for alkyne semi-hydrogenation, providing an effective strategy for stimulating low active Ni-based catalysts for other selective hydrogenations in industry.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532953","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}
Yutao Rao, Jiyeon Lee, Jinchao Chen, Ling Xu, Mingbo Zhou, Bangshao Yin, Jiwon Kim, Atsuhiro Osuka, Jianxin Song
5,18-Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5-dibromo-BODIPY with a-(pyro-2-ly)dipyrrin as the first examples of meso-aryl-substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11'-linked dimer, a cyclooctatetraene(COT)-centered trimer, and a spiro-trimer. Fused COT-centered 3H-orangarin dimer was oxidized to the corresponding 2H-orangarin dimer, which was further coupled to give a triply COT centered 2H-orangarin tetramer. 3H-Orangarin oligomers are all antiaromatic as evinced by extremely low-field-shifted 1H NMR signals of the inner NH and ill-defined absorption spectra with broad tails. In contrast, COT-centered 2H-orangarin dimer and tetramer show moderately low-field-shifted NH signals and intense NIR absorbance over 900 nm, suggesting the effective p-conjugation through the COT bridge and almost non-antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited-state decays.
{"title":"5,18-Dimesitylorangarin: a Stable Antiaromatic [20]Pentaphyrin(1.0.1.0.0) Displaying Remarkable Oxidative Self-Coupling Reactions.","authors":"Yutao Rao, Jiyeon Lee, Jinchao Chen, Ling Xu, Mingbo Zhou, Bangshao Yin, Jiwon Kim, Atsuhiro Osuka, Jianxin Song","doi":"10.1002/anie.202409655","DOIUrl":"https://doi.org/10.1002/anie.202409655","url":null,"abstract":"<p><p>5,18-Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5-dibromo-BODIPY with a-(pyro-2-ly)dipyrrin as the first examples of meso-aryl-substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11'-linked dimer, a cyclooctatetraene(COT)-centered trimer, and a spiro-trimer. Fused COT-centered 3H-orangarin dimer was oxidized to the corresponding 2H-orangarin dimer, which was further coupled to give a triply COT centered 2H-orangarin tetramer. 3H-Orangarin oligomers are all antiaromatic as evinced by extremely low-field-shifted 1H NMR signals of the inner NH and ill-defined absorption spectra with broad tails. In contrast, COT-centered 2H-orangarin dimer and tetramer show moderately low-field-shifted NH signals and intense NIR absorbance over 900 nm, suggesting the effective p-conjugation through the COT bridge and almost non-antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited-state decays.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141537106","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}
Organic scintillators are praised for their abundant element reserves, facile preparation procedures, and rich structures. Herein, a new family of highly efficient organic phosphonium halide salts with thermally activated delayed fluorescence (TADF) are designed by innovatively adopting quaternary phosphonium as the electron acceptor, while dimethylamine group and halide anions (I-) serve as the electron donor. The prepared butyl(2-[2-(dimethylamino)phenyl]phenyl)diphenylphosphonium iodide (C4-I) exhibits bright blue emission and an ultra-high photoluminescence quantum yield (PLQY) of 100%. Efficient charge transfer is realized through the unique n-π and anion-π stacking in solid-state C4-I. Photophysical studies of C4-I suggest that the incorporation of I accounts for high intersystem crossing rate (kISC) and reverse intersystem crossing rate (kRISC), suppressing the intrinsic prompt fluorescence and enabling near-pure TADF emission at room temperature. Benefitting from the large Stokes shift, high PLQY, efficient exciton utilization, and remarkable X-ray attenuation ability endowed by I, C4-I delivers an outstanding light yield of 80721 photons/MeV and a low limit of detection (LoD) of 22.79 nGy·s-1. This work would provide a rational design concept and open up an appealing road for developing efficient organic scintillators with tunable emission, strong X-ray attenuation ability, and excellent scintillator performance.
有机闪烁体以其丰富的元素储备、简便的制备程序和丰富的结构而备受赞誉。本文创新性地采用季鏻作为电子受体,二甲胺基团和卤化阴离子(I-)作为电子供体,设计出了一系列新型高效热激活延迟荧光(TADF)有机卤化鏻盐。所制备的丁基(2-[2-(二甲基氨基)苯基]苯基)二苯基碘化鏻(C4-I)具有明亮的蓝色发射光谱和 100% 的超高光量子产率(PLQY)。固态 C4-I 中独特的 n-π 和阴离子-π 堆叠实现了高效的电荷转移。对 C4-I 的光物理研究表明,I 的掺入导致了较高的系统间交叉率(kISC)和反向系统间交叉率(kRISC),从而抑制了固有的瞬时荧光,并在室温下实现了近乎纯净的 TADF 发射。得益于 I 所具有的大斯托克斯偏移、高 PLQY、高效激子利用率和出色的 X 射线衰减能力,C4-I 的光产率高达 80721 光子/兆电子伏,探测极限(LoD)低至 22.79 nGy-s-1。这项研究为开发具有可调发射、强 X 射线衰减能力和优异闪烁体性能的高效有机闪烁体提供了合理的设计理念,开辟了一条具有吸引力的道路。
{"title":"Phosphonium Iodide Featuring Blue Thermally Activated Delayed Fluorescence for Highly Efficient X-ray Scintillator.","authors":"Jun-Hua Wei, Jian-Bin Luo, Zi-Lin He, Qing-Peng Peng, Jing-Hua Chen, Zhi-Zhong Zhang, Xiu-Xian Guo, Dai-Bin Kuang","doi":"10.1002/anie.202410514","DOIUrl":"https://doi.org/10.1002/anie.202410514","url":null,"abstract":"<p><p>Organic scintillators are praised for their abundant element reserves, facile preparation procedures, and rich structures. Herein, a new family of highly efficient organic phosphonium halide salts with thermally activated delayed fluorescence (TADF) are designed by innovatively adopting quaternary phosphonium as the electron acceptor, while dimethylamine group and halide anions (I-) serve as the electron donor. The prepared butyl(2-[2-(dimethylamino)phenyl]phenyl)diphenylphosphonium iodide (C4-I) exhibits bright blue emission and an ultra-high photoluminescence quantum yield (PLQY) of 100%. Efficient charge transfer is realized through the unique n-π and anion-π stacking in solid-state C4-I. Photophysical studies of C4-I suggest that the incorporation of I accounts for high intersystem crossing rate (kISC) and reverse intersystem crossing rate (kRISC), suppressing the intrinsic prompt fluorescence and enabling near-pure TADF emission at room temperature. Benefitting from the large Stokes shift, high PLQY, efficient exciton utilization, and remarkable X-ray attenuation ability endowed by I, C4-I delivers an outstanding light yield of 80721 photons/MeV and a low limit of detection (LoD) of 22.79 nGy·s-1. This work would provide a rational design concept and open up an appealing road for developing efficient organic scintillators with tunable emission, strong X-ray attenuation ability, and excellent scintillator performance.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532886","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}
Herein, we describe an innovative approach to the asymmetric electrochemical α-alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α-alkylation of aldehydes. Additionally, this novel catalyst exhibits enhanced catalytic activity and excellent stereoselective control comparable to conventional catalytic systems. As a result, this strategy provides a new avenue for versatile asymmetric electrochemistry. The electrooxidation of diverse phenols enables the C-H/C-H oxidative α-alkylation of aldehydes in a highly chemo- and stereoselective fashion. Detailed mechanistic studies by control experiments and cyclic voltammetry analysis demonstrate possible reaction pathways and the origin of enantio-induction.
{"title":"Bifunctional Chiral Electrocatalysts Enable Enantioselective α-Alkylation of Aldehydes.","authors":"Jin-Yu He, Cuiju Zhu, Wen-Xi Duan, Ling-Xuan Kong, Na-Na Wang, Yan-Zhao Wang, Zhi-Yong Fan, Xin-Ying Qiao, Hao Xu","doi":"10.1002/anie.202401355","DOIUrl":"https://doi.org/10.1002/anie.202401355","url":null,"abstract":"<p><p>Herein, we describe an innovative approach to the asymmetric electrochemical α-alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α-alkylation of aldehydes. Additionally, this novel catalyst exhibits enhanced catalytic activity and excellent stereoselective control comparable to conventional catalytic systems. As a result, this strategy provides a new avenue for versatile asymmetric electrochemistry. The electrooxidation of diverse phenols enables the C-H/C-H oxidative α-alkylation of aldehydes in a highly chemo- and stereoselective fashion. Detailed mechanistic studies by control experiments and cyclic voltammetry analysis demonstrate possible reaction pathways and the origin of enantio-induction.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532951","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 present a series of borane-tethered cyclic (alkyl)(amino)carbene (cAAC)-copper complexes, including a borane-capped Cu(I) hydride. This hydride is unusually hydridic and reacts rapidly with both CO2 and 2,6-dimethylphenol at room temperature. Its reactivity is distinct from variants without a tethered borane, and the underlying principles governing the enhanced hydricity were evaluated experimentally and theoretically. These stoichiometric results were extended to catalytic CO2 hydrogenation, and the borane-tethered (intramolecular) system exhibits ~3-fold enhancement relative to an intermolecular system.
我们展示了一系列硼烷系环(烷基)(氨基)碳化物(cAAC)-铜配合物,其中包括一种硼烷封端的氢化物 Cu(I)。这种氢化物具有非同寻常的水合性,可在室温下与二氧化碳和 2,6-二甲基苯酚迅速反应。它的反应性与没有硼烷系链的变体截然不同,而且实验和理论都对增强水合性的基本原理进行了评估。这些化学计量学结果被推广到催化 CO2 加氢反应中,与分子间体系相比,硼烷系链(分子内)体系的水合性提高了约 3 倍。
{"title":"Lewis Acid-Tethered (cAAC)-Copper Complexes: Reactivity for Hydride Transfer and Catalytic CO2 Hydrogenation.","authors":"Hayoung Song, Nathaniel Kolnik Szymczak","doi":"10.1002/anie.202411099","DOIUrl":"https://doi.org/10.1002/anie.202411099","url":null,"abstract":"<p><p>We present a series of borane-tethered cyclic (alkyl)(amino)carbene (cAAC)-copper complexes, including a borane-capped Cu(I) hydride. This hydride is unusually hydridic and reacts rapidly with both CO2 and 2,6-dimethylphenol at room temperature. Its reactivity is distinct from variants without a tethered borane, and the underlying principles governing the enhanced hydricity were evaluated experimentally and theoretically. These stoichiometric results were extended to catalytic CO2 hydrogenation, and the borane-tethered (intramolecular) system exhibits ~3-fold enhancement relative to an intermolecular system.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532885","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}
Zhipeng Zhang, Lu Qian, Bin Zhang, Chunfeng Ma, Guangzhao Zhang
Ionogels are promising for soft iontronics, with their network structure playing a pivotal role in determining their performance and potential applications. However, simultaneously achieving mechanical toughness, low hysteresis, self-healing, and fluorescence using existing network structures is challenging. Drawing inspiration from jellyfish, we propose a novel hierarchical crosslinking network structure design for in situ formation of hyperbranched cluster aggregates (HCA) to fabricate polyurea ionogels to overcome these challenges. Leveraging the disparate reactivity of isocyanate groups, we induce the in situ formation of HCA through competing reactions, enhancing toughness and imparting the clustering-triggered emission of ionogel. This synergy between supramolecular interactions in the network and plasticizing effect in ionic liquid leads to reduced hysteresis of the ionogel. Furthermore, the incorporation of NCO-terminated prepolymer with dynamic oxime-urethane bonds (NPU) enables self-healing and enhances stretchability. Our investigations highlight the significant influence of HCA on ionogel performance, showcasing mechanical robustness including high strength (3.5 MPa), exceptional toughness (5.5 MJ m-3), resistance to puncture, and low hysteresis, self-healing, as well as fluorescence, surpassing conventional dynamic crosslinking approaches. This network design strategy is versatile and can meet the various demands of flexible electronics applications.
{"title":"Jellyfish-inspired Polyurea Ionogel with Mechanical Robustness, Self-Healing, and Fluorescence Enabled by Hyperbranched Cluster Aggregates.","authors":"Zhipeng Zhang, Lu Qian, Bin Zhang, Chunfeng Ma, Guangzhao Zhang","doi":"10.1002/anie.202410335","DOIUrl":"https://doi.org/10.1002/anie.202410335","url":null,"abstract":"<p><p>Ionogels are promising for soft iontronics, with their network structure playing a pivotal role in determining their performance and potential applications. However, simultaneously achieving mechanical toughness, low hysteresis, self-healing, and fluorescence using existing network structures is challenging. Drawing inspiration from jellyfish, we propose a novel hierarchical crosslinking network structure design for in situ formation of hyperbranched cluster aggregates (HCA) to fabricate polyurea ionogels to overcome these challenges. Leveraging the disparate reactivity of isocyanate groups, we induce the in situ formation of HCA through competing reactions, enhancing toughness and imparting the clustering-triggered emission of ionogel. This synergy between supramolecular interactions in the network and plasticizing effect in ionic liquid leads to reduced hysteresis of the ionogel. Furthermore, the incorporation of NCO-terminated prepolymer with dynamic oxime-urethane bonds (NPU) enables self-healing and enhances stretchability. Our investigations highlight the significant influence of HCA on ionogel performance, showcasing mechanical robustness including high strength (3.5 MPa), exceptional toughness (5.5 MJ m-3), resistance to puncture, and low hysteresis, self-healing, as well as fluorescence, surpassing conventional dynamic crosslinking approaches. This network design strategy is versatile and can meet the various demands of flexible electronics applications.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532954","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}
Mechanochromic functionality realized via the force-responsive mechanophores in polymers has great potential for damage sensing and information storage. Mechanophores with the ability to recognize multiple stimuli for tunable chromic characteristics are highly sought after for versatile sensing ability and color programmability. Nevertheless, the majority of mechanophores are based on single-component chromophores with limited sensitivity, or require additional fabrication technology for multi-modal chromism. Here, we report a novel multifunctional mechanophore capable of vividly detectable and tunable mechanochromism in polymers. This synergistic optical coupling relies on strategically fusing rhodamine and spiropyran (Rh-SP), and tethering polymer chains on both subunits. The mechanochromic behaviors of the Rh-SP-linked polymers under sonication and compression are thoroughly evaluated in response to changes in force and the light-controlled relaxation process. Non-sequential ring-opening of the two subunits under force is identified, endowing high-contrast mechanochromism. Light-induced differential ring-closing reactions of the two subunits, together with the acidichromism of the SP moiety, are employed to engineer elastomers with programmable and wide-spectrum colors. Our work presents an effective strategy for highly appreciable and regulable mechanochromic functionality, and also provides new insights into the rupture mechanisms of π-fused mechanophores, as well as how the stimuli history controls stress accumulation in polymers.
{"title":"A Rhodamine-Spiropyran Conjugate Empowering Tunable Mechanochromism in Polymers under Multiple Stimuli.","authors":"Ze-Ying Sun, Yiran Li, Mengjiao Wu, Weiye He, Yuan Yuan, Yi Cao, Yulan Chen","doi":"10.1002/anie.202411629","DOIUrl":"https://doi.org/10.1002/anie.202411629","url":null,"abstract":"<p><p>Mechanochromic functionality realized via the force-responsive mechanophores in polymers has great potential for damage sensing and information storage. Mechanophores with the ability to recognize multiple stimuli for tunable chromic characteristics are highly sought after for versatile sensing ability and color programmability. Nevertheless, the majority of mechanophores are based on single-component chromophores with limited sensitivity, or require additional fabrication technology for multi-modal chromism. Here, we report a novel multifunctional mechanophore capable of vividly detectable and tunable mechanochromism in polymers. This synergistic optical coupling relies on strategically fusing rhodamine and spiropyran (Rh-SP), and tethering polymer chains on both subunits. The mechanochromic behaviors of the Rh-SP-linked polymers under sonication and compression are thoroughly evaluated in response to changes in force and the light-controlled relaxation process. Non-sequential ring-opening of the two subunits under force is identified, endowing high-contrast mechanochromism. Light-induced differential ring-closing reactions of the two subunits, together with the acidichromism of the SP moiety, are employed to engineer elastomers with programmable and wide-spectrum colors. Our work presents an effective strategy for highly appreciable and regulable mechanochromic functionality, and also provides new insights into the rupture mechanisms of π-fused mechanophores, as well as how the stimuli history controls stress accumulation in polymers.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532950","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}
Lin Wu, Xilin Mu, Denghui Liu, Wei Li, Deli Li, Jiasen Zhang, Chunyu Liu, Tingting Feng, Yujie Wu, Jiuyan Li, Shi-Jian Su, Ziyi Ge
Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through distinct segments of the molecule. Three novel blue emitters A-BN, DA-BN, and A-DBN, have been successfully synthesized by integrating highly rigid and three-dimensional adamantane-containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: part 1 comprises a boron-nitrogen (BN)-MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; part 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three-dimensional "umbrella-like" conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A-BN, DA-BN, and A-DBN exhibit remarkably narrow FWHM values ranging from 18 to 14 nm and near-unity photoluminescence quantum yields. Particularly, OLEDs based on DA-BN and A-DBN demonstrate outstanding efficiencies of 35.0% and 34.3%, with FWHM values as low as 22 nm and 25 nm, respectively, effectively accomplishing the integration of high color purity and high device performance.
{"title":"Regional Functionalization Molecular Design Strategy: A Key to Enhancing the Efficiency of Multi-Resonance OLEDs.","authors":"Lin Wu, Xilin Mu, Denghui Liu, Wei Li, Deli Li, Jiasen Zhang, Chunyu Liu, Tingting Feng, Yujie Wu, Jiuyan Li, Shi-Jian Su, Ziyi Ge","doi":"10.1002/anie.202409580","DOIUrl":"https://doi.org/10.1002/anie.202409580","url":null,"abstract":"<p><p>Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through distinct segments of the molecule. Three novel blue emitters A-BN, DA-BN, and A-DBN, have been successfully synthesized by integrating highly rigid and three-dimensional adamantane-containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: part 1 comprises a boron-nitrogen (BN)-MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; part 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three-dimensional \"umbrella-like\" conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A-BN, DA-BN, and A-DBN exhibit remarkably narrow FWHM values ranging from 18 to 14 nm and near-unity photoluminescence quantum yields. Particularly, OLEDs based on DA-BN and A-DBN demonstrate outstanding efficiencies of 35.0% and 34.3%, with FWHM values as low as 22 nm and 25 nm, respectively, effectively accomplishing the integration of high color purity and high device performance.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141537147","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}
Giacomo Renno, Dongping Chen, Qing-Xia Zhang, Rosa M Gomila, Antonio Frontera, Naomi Sakai, Thomas R Ward, Stefan Matile
The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a s-hole interaction that is essentially absent in biocatalysis. For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate. Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the s hole on the Sb(V) center, and the emergence of saturation kinetic behavior. Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition. Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product. The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis.
本研究的目的是创建人工酶,利用生物催化中基本不存在的 s 孔相互作用--pnictogen 键。 为此,我们在 stibine 催化剂上添加了生物素衍生物,并将其与链霉亲和素突变体相结合,以确定一种高效的转移氢化催化剂,用于还原含氟喹啉底物。 从野生型链霉亲和素到最佳突变体催化活性的提高与 Sb(V)中心 s 孔的深度以及饱和动力学行为的出现相吻合。 迈克尔斯-门顿分析表明,过渡态的识别能力在低微摩尔范围内,比毫摩尔底物识别能力强三个数量级以上。 最佳突变体偏好的羧酸盐通过氢键离子配对和阴离子-π与新出现的吡啶产物的相互作用,促进了过渡态识别。 水性体系中出现的具有挑战性的立体选择性进一步强调了吡啶鎓键与高阶体系催化的兼容性。
{"title":"Pnictogen-Bonding Enzymes.","authors":"Giacomo Renno, Dongping Chen, Qing-Xia Zhang, Rosa M Gomila, Antonio Frontera, Naomi Sakai, Thomas R Ward, Stefan Matile","doi":"10.1002/anie.202411347","DOIUrl":"https://doi.org/10.1002/anie.202411347","url":null,"abstract":"<p><p>The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a s-hole interaction that is essentially absent in biocatalysis. For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate. Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the s hole on the Sb(V) center, and the emergence of saturation kinetic behavior. Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition. Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product. The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532887","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}