Ernesto A Hernández-Morales,Dayra Barreto-Hernández,Dazaet Galicia-Badillo,Rubén A Toscano,M Elena García-Aguilera,Braulio Rodríguez-Molina
Harnessing mechanical motion in molecular crystals is a critical goal for developing novel energy conversion materials. Among known strategies, the ejection of guest molecules from the lattice via the jumping-mate approach offers a direct means of propulsion. Here, we present isostructural cocrystals of indolo[3,2-a]carbazole (ICZ) and (E)-1,2-di(pyridin-4-yl)ethene (BPE) that incorporate solvents such as acetone, ethyl acetate, or tetrahydrofuran. X-ray diffraction and solid-state nuclear magnetic resonance (NMR) studies confirmed the presence of solvents or solvent mixtures. Upon heating, these channel-type cocrystals exhibit a thermosalient effect, with temperature regulation achieved by releasing pure or solvent mixtures. Differential scanning calorimetry and thermogravimetry (DSC-TGA) analyses revealed that the transition temperatures changed progressively, demonstrating controllable thermal actuation through the release of occluded solvents. This work demonstrates a simple yet powerful way to regulate mechanical responses in molecular crystals, thereby advancing the design of responsive energy conversion materials.
{"title":"Crystals as Rockets: Modulation of the Salient Temperature in Cocrystals by Solvent Mixture Composition.","authors":"Ernesto A Hernández-Morales,Dayra Barreto-Hernández,Dazaet Galicia-Badillo,Rubén A Toscano,M Elena García-Aguilera,Braulio Rodríguez-Molina","doi":"10.1002/anie.202526010","DOIUrl":"https://doi.org/10.1002/anie.202526010","url":null,"abstract":"Harnessing mechanical motion in molecular crystals is a critical goal for developing novel energy conversion materials. Among known strategies, the ejection of guest molecules from the lattice via the jumping-mate approach offers a direct means of propulsion. Here, we present isostructural cocrystals of indolo[3,2-a]carbazole (ICZ) and (E)-1,2-di(pyridin-4-yl)ethene (BPE) that incorporate solvents such as acetone, ethyl acetate, or tetrahydrofuran. X-ray diffraction and solid-state nuclear magnetic resonance (NMR) studies confirmed the presence of solvents or solvent mixtures. Upon heating, these channel-type cocrystals exhibit a thermosalient effect, with temperature regulation achieved by releasing pure or solvent mixtures. Differential scanning calorimetry and thermogravimetry (DSC-TGA) analyses revealed that the transition temperatures changed progressively, demonstrating controllable thermal actuation through the release of occluded solvents. This work demonstrates a simple yet powerful way to regulate mechanical responses in molecular crystals, thereby advancing the design of responsive energy conversion materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"77 1","pages":"e26010"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471507","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}
Swapnil Ghule,Sayan Sarkar,Maria Eugenia Pérez-Ojeda Rodriguez,Mark Spector,Frank Hampel,Evgeny A Kataev
The design of supramolecular receptors for amino acids presents a fundamentally challenging yet highly promising avenue of research. Phenylalanine attracts special attention because of its multifaceted role in living organisms. Although many synthetic hosts have been explored for recognition of phenylalanine (Phe), besides cucurbiturils, there are no receptors that show selectivity for Phe over other aromatic amino acids and related aromatic neurotransmitters in water. Toward addressing this challenge, we explored pi-conjugated water-soluble macrocycles with hydrophobic pockets. A new family of o-terphenyl-based macrocycles, TP[n] (n = 2-8) was synthesized using the Yamamoto reaction. Macrocycles up to the octamer, TP[2]-TP[8], were isolated and fully characterized. X-ray studies reveal that these macrocycles can form folded conformations stabilized by stacking interactions. TP[3] was identified as the most selective host for Phe with an affinity of 7 x 103 M-1 in water. The hosts, composed of 2-5 subunits were found to effectively inhibit protein aggregation according to the fluorescence assay using thioflavin T. The discovery of the new family of macrocycles paves the way for designing hosts with diverse architectures, precisely tailored geometries, and optimized binding properties capable of targeting not only individual amino acids but also entire protein surfaces.
{"title":"o-Terphenyl-Based Family of Conjugated Macrocycles: Selective Recognition of Phenylalanine in Water and Interaction With Insulin.","authors":"Swapnil Ghule,Sayan Sarkar,Maria Eugenia Pérez-Ojeda Rodriguez,Mark Spector,Frank Hampel,Evgeny A Kataev","doi":"10.1002/anie.202525972","DOIUrl":"https://doi.org/10.1002/anie.202525972","url":null,"abstract":"The design of supramolecular receptors for amino acids presents a fundamentally challenging yet highly promising avenue of research. Phenylalanine attracts special attention because of its multifaceted role in living organisms. Although many synthetic hosts have been explored for recognition of phenylalanine (Phe), besides cucurbiturils, there are no receptors that show selectivity for Phe over other aromatic amino acids and related aromatic neurotransmitters in water. Toward addressing this challenge, we explored pi-conjugated water-soluble macrocycles with hydrophobic pockets. A new family of o-terphenyl-based macrocycles, TP[n] (n = 2-8) was synthesized using the Yamamoto reaction. Macrocycles up to the octamer, TP[2]-TP[8], were isolated and fully characterized. X-ray studies reveal that these macrocycles can form folded conformations stabilized by stacking interactions. TP[3] was identified as the most selective host for Phe with an affinity of 7 x 103 M-1 in water. The hosts, composed of 2-5 subunits were found to effectively inhibit protein aggregation according to the fluorescence assay using thioflavin T. The discovery of the new family of macrocycles paves the way for designing hosts with diverse architectures, precisely tailored geometries, and optimized binding properties capable of targeting not only individual amino acids but also entire protein surfaces.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":"e25972"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471501","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}
Copper-based catalysts are widely regarded as promising candidates for electrocatalytic nitrate reduction (NO3RR), an environmentally benign route to ammonia synthesis, yet their efficiency is often constrained by nitrite accumulation and insufficient active hydrogen (*H) supply at high current densities. Here, isolated Cu atoms were anchored into a hollow Co3S4 polyhedral framework (Cu-Co3S4), generating a sulfur bridged asymmetric active center. Electrochemical and computational studies reveal that Co3S4 functions as an efficient *H donor, transferring hydrogen species to Cu sites through a sulfur bridge mediated reverse hydrogen spillover process, thereby accelerating the hydrogenation of nitrogen intermediates. By precisely tuning the Cu site density to balance nitrogen intermediate adsorption with *H supply, the optimized Cu1.01wt%-Co3S4 catalyst delivers an exceptional NH3 yield rate of 94.52 mg h-1 mgcat. -1 (18.90 mg h-1 cm-2) and a Faradaic efficiency (FE) of 95.18% at -0.8 V vs reversible hydrogen electrode. The catalyst also exhibits remarkable durability over 300 h at -200 mA cm-2 and performs effectively in zinc-nitrate batteries. These findings highlight the importance of coupling intermediate activation with hydrogenation kinetics and provide guiding principles for the rational design of high efficiency NO3RR electrocatalysts.
铜基催化剂被广泛认为是电催化硝酸还原（NO3RR）的有希望的候选者，这是一种环保的氨合成途径，但它们的效率往往受到亚硝酸盐积累和高电流密度下活性氢（*H）供应不足的限制。在这里，孤立的Cu原子被锚定在一个中空的Co3S4多面体框架（Cu-Co3S4）中，产生一个硫桥接的不对称活性中心。电化学和计算研究表明，Co3S4作为一个有效的*H供体，通过硫桥介导的逆向氢溢出过程将氢转移到Cu位点，从而加速氮中间体的加氢。通过精确调整Cu位点密度来平衡氮中间体吸附和*H供应，优化后的Cu1.01wt%-Co3S4催化剂的NH3产率达到了94.52 mg H -1 mgcat。在-0.8 V vs可逆氢电极下，-1 （18.90 mg h-1 cm-2）和95.18%的法拉第效率（FE）。该催化剂在-200 mA cm-2下具有300小时以上的耐久性，并在硝酸锌电池中具有良好的性能。这些发现突出了中间活化与加氢动力学耦合的重要性，为合理设计高效NO3RR电催化剂提供了指导原则。
{"title":"Sulfur-Bridge Engineering Enables Reverse Hydrogen Spillover to Atomic Cu for Nitrate-to-Ammonia Electrocatalysis.","authors":"Ruonan Li,Runlin Ma,Li-Li Zhang,Menggai Jiao,Zhen Zhou","doi":"10.1002/anie.7688164","DOIUrl":"https://doi.org/10.1002/anie.7688164","url":null,"abstract":"Copper-based catalysts are widely regarded as promising candidates for electrocatalytic nitrate reduction (NO3RR), an environmentally benign route to ammonia synthesis, yet their efficiency is often constrained by nitrite accumulation and insufficient active hydrogen (*H) supply at high current densities. Here, isolated Cu atoms were anchored into a hollow Co3S4 polyhedral framework (Cu-Co3S4), generating a sulfur bridged asymmetric active center. Electrochemical and computational studies reveal that Co3S4 functions as an efficient *H donor, transferring hydrogen species to Cu sites through a sulfur bridge mediated reverse hydrogen spillover process, thereby accelerating the hydrogenation of nitrogen intermediates. By precisely tuning the Cu site density to balance nitrogen intermediate adsorption with *H supply, the optimized Cu1.01wt%-Co3S4 catalyst delivers an exceptional NH3 yield rate of 94.52 mg h-1 mgcat. -1 (18.90 mg h-1 cm-2) and a Faradaic efficiency (FE) of 95.18% at -0.8 V vs reversible hydrogen electrode. The catalyst also exhibits remarkable durability over 300 h at -200 mA cm-2 and performs effectively in zinc-nitrate batteries. These findings highlight the importance of coupling intermediate activation with hydrogenation kinetics and provide guiding principles for the rational design of high efficiency NO3RR electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":"e7688164"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471505","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}
“My science “heroes” are all my supervisors, mentors, collaborators, and students because they always blow my mind…Chemistry is fun because it allows me to see the unseen…”
{"title":"Isaac Choi","authors":"Isaac Choi","doi":"10.1002/anie.8165954","DOIUrl":"https://doi.org/10.1002/anie.8165954","url":null,"abstract":"“<i>My science “heroes” are all my supervisors, mentors, collaborators, and students because they always blow my mind…Chemistry is fun because it allows me to see the unseen…”</i>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478811","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}
Yanjiang Chen, Ying Ye, Hui Zhou, Yuchen Zhang, Juan Fan, Huiying Sun, Genhui Chen, Yuanyuan Wang, Yuqiao Zhou, Dong Zhang
Herein, we report an efficient metal‐free and redox‐neutral electrochemical strategy for the cis ‐selective cyclopropanation of less active alkenes with sulfoxonium ylides. This protocol circumvents the limitations of traditional methods, which are typically restricted to electron‐deficient alkenes, and provides access to thermodynamically less stable cis ‐cyclopropanes. Furthermore, the resulting cyclopropanes can be readily diverted to hydroalkylation products via controlled cathodic reductive ring‐opening. Mechanistic studies support a radical cation‐mediated stepwise cycloaddition pathway, wherein the cis ‐diastereoselectivity is established during the initial radical addition. This sustainable approach not only broadens the synthetic utility of sulfoxonium ylides but also represents a significant advance in green electrochemical synthesis.
{"title":"Redox‐Neutral Electrochemical Cis ‐Cyclopropanation of Alkenes With Sulfoxonium Ylides","authors":"Yanjiang Chen, Ying Ye, Hui Zhou, Yuchen Zhang, Juan Fan, Huiying Sun, Genhui Chen, Yuanyuan Wang, Yuqiao Zhou, Dong Zhang","doi":"10.1002/anie.7024568","DOIUrl":"https://doi.org/10.1002/anie.7024568","url":null,"abstract":"Herein, we report an efficient metal‐free and redox‐neutral electrochemical strategy for the <jats:italic>cis</jats:italic> ‐selective cyclopropanation of less active alkenes with sulfoxonium ylides. This protocol circumvents the limitations of traditional methods, which are typically restricted to electron‐deficient alkenes, and provides access to thermodynamically less stable <jats:italic>cis</jats:italic> ‐cyclopropanes. Furthermore, the resulting cyclopropanes can be readily diverted to hydroalkylation products via controlled cathodic reductive ring‐opening. Mechanistic studies support a radical cation‐mediated stepwise cycloaddition pathway, wherein the <jats:italic>cis</jats:italic> ‐diastereoselectivity is established during the initial radical addition. This sustainable approach not only broadens the synthetic utility of sulfoxonium ylides but also represents a significant advance in green electrochemical synthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"273 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471674","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}
Achieving 2,5-diformylfuran (DFF), a key green biomass plastic monomer, from conventional oxidation of 5-hydroxymethylfurfural (HMF) often involves harsh conditions such as strong alkaline media and is prone to base-catalyzed polymerization side reactions. Herein, we engineered both bulk compression and surface tension strain in rhodium nanoclusters-modified cadmium sulfide nanorods through aluminum doping (Al/RhNC-CdS) to boost highly selective anaerobic photocatalytic coproduction of DFF and hydrogen from neutral HMF aqueous solutions under mild conditions. In situ characterization combined with first-principles simulation proves that the bulk compression strain significantly enhances the photogenerated charge separation in Al/RhNC-CdS, while the surface tension strain facilitates the rate-determining dehydrogenation oxidation of HMF into the key *C6H5O3 intermediate. These unique characteristics enables Al/RhNC-CdS to achieve a 17-, 9-, and 4-fold higher H2 (776.8 µmol g- 1 h- 1) and DFF yield (745.9 µmol g- 1 h- 1, with 94.8% selectivity) compared to CdS modified with conventional Rh nanoparticles, nanoclusters, or single atoms. This strain-induced activity enhancement is also observed in other metal nanocluster-loaded CdS systems, highlighting the universal applicability of the proposed strategy. More significantly, Al/RhNC-CdS exhibited remarkable yields toward H2 (270.9 µmol g- 1 h- 1) and DFF (255.3 µmol g- 1 h- 1, with 95.4% selectivity) in an outdoor concentrated solar-driven photocatalytic system, thus verifying its feasibility for large-scale manufacturing.
{"title":"Engineering Bulk Compression and Surface Tension Strains Toward Anaerobic 5-Hydroxymethylfurfural Photoconversion.","authors":"Huanmin Liu,Xu Zhang,Kun Zheng,Wei Wang,Xiaomin Lao,Xinyu Song,Yitong Liu,Chao Wu,Dingguo Tang,Kangle Lv,Qin Li,Peng Zhou","doi":"10.1002/anie.6400652","DOIUrl":"https://doi.org/10.1002/anie.6400652","url":null,"abstract":"Achieving 2,5-diformylfuran (DFF), a key green biomass plastic monomer, from conventional oxidation of 5-hydroxymethylfurfural (HMF) often involves harsh conditions such as strong alkaline media and is prone to base-catalyzed polymerization side reactions. Herein, we engineered both bulk compression and surface tension strain in rhodium nanoclusters-modified cadmium sulfide nanorods through aluminum doping (Al/RhNC-CdS) to boost highly selective anaerobic photocatalytic coproduction of DFF and hydrogen from neutral HMF aqueous solutions under mild conditions. In situ characterization combined with first-principles simulation proves that the bulk compression strain significantly enhances the photogenerated charge separation in Al/RhNC-CdS, while the surface tension strain facilitates the rate-determining dehydrogenation oxidation of HMF into the key *C6H5O3 intermediate. These unique characteristics enables Al/RhNC-CdS to achieve a 17-, 9-, and 4-fold higher H2 (776.8 µmol g- 1 h- 1) and DFF yield (745.9 µmol g- 1 h- 1, with 94.8% selectivity) compared to CdS modified with conventional Rh nanoparticles, nanoclusters, or single atoms. This strain-induced activity enhancement is also observed in other metal nanocluster-loaded CdS systems, highlighting the universal applicability of the proposed strategy. More significantly, Al/RhNC-CdS exhibited remarkable yields toward H2 (270.9 µmol g- 1 h- 1) and DFF (255.3 µmol g- 1 h- 1, with 95.4% selectivity) in an outdoor concentrated solar-driven photocatalytic system, thus verifying its feasibility for large-scale manufacturing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":"e6400652"},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465025","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}
Shuangshuang Xiong, Sijie Yuan, Junru Li, Hendrik F. T. Klare, Martin Oestreich, Tao He
A “bioinspired” silylarylation of unactivated terminal alkenes involving formal thiosilylation of the C═C double bond followed by an intramolecular electrophilic aromatic substitution (S E Ar) is disclosed. The reaction is initiated by weak coordination of a silylium ion to the terminal alkene to form a β‐silicon‐stabilized carbenium ion that is subsequently captured by an external sulfide co‐catalyst to yield a sulfonium‐ion electrophile. Nucleophilic attack of the tethered arene then affords a highly Brønsted acidic arenium ion, which allows for protodearylation of an arylsilane additive for the regeneration of the silylium ion stabilized by the sulfur donor. This step is also modulated by the sulfide donor as a proton shuttle thereby mitigating side reactions such as competing hydroarylation or alkene oligomerization. This ionic alkene silylarylation is a silylium‐ion‐mediated reaction where a sulfide co‐catalyst balances the reactivities of the involved cationic intermediates, eventually improving the overall efficiency of the process.
公开了一种非活化末端烯烃的“生物启发”硅烷化，涉及C = C双键的形式硫代硅烷化，随后是分子内亲电芳取代（S E Ar）。该反应由硅离子与末端烯烃弱配位引发，形成β -硅稳定的碳离子，随后被外部硫化物共催化剂捕获，生成硫离子亲电试剂。拴系芳烃的亲核性攻击提供了一个高度Brønsted的酸性arenium离子，这允许芳基硅烷添加剂的原酰化，从而使由硫供体稳定的硅离子再生。这一步骤也由硫化物供体作为质子穿梭体调节，从而减轻副反应，如竞争性氢化芳基化或烯烃寡聚化。这种离子烯烃硅芳基化反应是一种硅离子介导的反应，其中硫化物共催化剂平衡了所涉及的阳离子中间体的反应活性，最终提高了整个过程的效率。
{"title":"Intramolecular Silylarylation of α‐Olefins Enabled by Disulfide Co‐Catalysis and Maintained by Proton‐into‐Silylium Interconversion","authors":"Shuangshuang Xiong, Sijie Yuan, Junru Li, Hendrik F. T. Klare, Martin Oestreich, Tao He","doi":"10.1002/anie.5903420","DOIUrl":"https://doi.org/10.1002/anie.5903420","url":null,"abstract":"A “bioinspired” silylarylation of unactivated terminal alkenes involving formal thiosilylation of the C═C double bond followed by an intramolecular electrophilic aromatic substitution (S <jats:sub>E</jats:sub> Ar) is disclosed. The reaction is initiated by weak coordination of a silylium ion to the terminal alkene to form a β‐silicon‐stabilized carbenium ion that is subsequently captured by an external sulfide co‐catalyst to yield a sulfonium‐ion electrophile. Nucleophilic attack of the tethered arene then affords a highly Brønsted acidic arenium ion, which allows for protodearylation of an arylsilane additive for the regeneration of the silylium ion stabilized by the sulfur donor. This step is also modulated by the sulfide donor as a proton shuttle thereby mitigating side reactions such as competing hydroarylation or alkene oligomerization. This ionic alkene silylarylation is a silylium‐ion‐mediated reaction where a sulfide co‐catalyst balances the reactivities of the involved cationic intermediates, eventually improving the overall efficiency of the process.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"14 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471516","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}
Hydrogen peroxide (H2O2) is a versatile and green oxidant with wide industrial applications, yet its large-scale production still relies on the energy-intensive anthraquinone process. Photocatalytic synthesis of H2O2 under visible light offers a sustainable alternative but remains limited by inefficient charge separation and mass transport in extended framework materials. Herein, we report the modular construction of two porphyrin-based double-cavity metallacages via orthogonal Pt(II)/carboxylate/pyridine and Zn-porphyrin/pyridine coordination. The resulting metallacages feature an intrinsic donor-acceptor architecture that promotes photoinduced electron transfer and charge separation. Encapsulation of electron-rich aromatic guests (triphenylene or benzotrithiophene) further stabilizes the charge-separated state and prolongs carrier lifetimes, thereby enhancing the photocatalytic H2O2 generation with a rate of 4037 µmol·g-1·h-1 in the presence of benzyl alcohol, among the highest reported values for visible-light supramolecular photocatalysts. This work establishes discrete metallacages and their host-guest complexes as an emerging platform for supramolecular photocatalysis and rational H2O2 photosynthesis, which will pave the way for the future development of metallacages in photocatalytic applications.
{"title":"Guest-Enhanced Charge Separation in Porphyrin-Based Double-Cavity Metallacages for Visible-Light-Driven H2O2 Production.","authors":"Yujuan Huang,Shijin Jian,Ziteng Guo,Zeyuan Zhang,Zhikai Li,Haonan Peng,Mingming Zhang","doi":"10.1002/anie.9964829","DOIUrl":"https://doi.org/10.1002/anie.9964829","url":null,"abstract":"Hydrogen peroxide (H2O2) is a versatile and green oxidant with wide industrial applications, yet its large-scale production still relies on the energy-intensive anthraquinone process. Photocatalytic synthesis of H2O2 under visible light offers a sustainable alternative but remains limited by inefficient charge separation and mass transport in extended framework materials. Herein, we report the modular construction of two porphyrin-based double-cavity metallacages via orthogonal Pt(II)/carboxylate/pyridine and Zn-porphyrin/pyridine coordination. The resulting metallacages feature an intrinsic donor-acceptor architecture that promotes photoinduced electron transfer and charge separation. Encapsulation of electron-rich aromatic guests (triphenylene or benzotrithiophene) further stabilizes the charge-separated state and prolongs carrier lifetimes, thereby enhancing the photocatalytic H2O2 generation with a rate of 4037 µmol·g-1·h-1 in the presence of benzyl alcohol, among the highest reported values for visible-light supramolecular photocatalysts. This work establishes discrete metallacages and their host-guest complexes as an emerging platform for supramolecular photocatalysis and rational H2O2 photosynthesis, which will pave the way for the future development of metallacages in photocatalytic applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":"e9964829"},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465019","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}
Dong Xie, Ran Liu, Ning Xu, Yangyang Song, Kangkang Sun, Wei‐Jin Gu, Wei Han
Anti‐Markovnikov oxidation of alkenes to access primary alcohols remains a significant synthetic challenge due to inherent regioselectivity constraints. Here we report a bio‐inspired iron catalyst bearing a cysteine‐derived ligand (BC t LOM) that enables radical hydroxyazidation of unconjugated tri‐, di‐, and monosubstituted alkenes with high anti‐Markovnikov selectivity. Utilizing TMSN 3 and hydrogen peroxide as azide source and oxidant, respectively, this method operates under mild conditions and tolerates diverse functional groups, including complex natural products and pharmaceuticals. Mechanistic studies suggest an iron‐oxo mediated radical pathway that suppresses competing epoxidation. This approach provides direct access to unprotected 2‐azido primary alcohols, versatile intermediates for further functionalization. The strategy expands the toolkit for selective alkene difunctionalization, offering potential applications in organic synthesis, chemical biology, and drug discovery.
由于固有的区域选择性限制，烯烃抗马尔可夫尼科夫氧化获得伯醇仍然是一个重大的合成挑战。在这里，我们报道了一种带有半胱氨酸衍生配体（BC - t - LOM）的生物激发铁催化剂，它能够对非共轭的三、二和单取代烯烃进行自由基羟基化，具有很高的抗马尔可夫尼科夫选择性。该方法以tms3和双氧水分别作为叠氮化物源和氧化剂，在温和的条件下运行，可耐受多种官能团，包括复杂的天然产物和药物。机制研究表明，铁-氧介导的自由基途径抑制竞争性环氧化。这种方法提供了直接接触无保护的2 -叠氮基伯醇，用于进一步功能化的多功能中间体。该策略扩展了选择性烯烃双官能化的工具箱，在有机合成、化学生物学和药物发现方面提供了潜在的应用。
{"title":"Iron‐Catalyzed Anti‐Markovnikov Hydroxyazidation of Unactivated Alkenes","authors":"Dong Xie, Ran Liu, Ning Xu, Yangyang Song, Kangkang Sun, Wei‐Jin Gu, Wei Han","doi":"10.1002/anie.5568728","DOIUrl":"https://doi.org/10.1002/anie.5568728","url":null,"abstract":"Anti‐Markovnikov oxidation of alkenes to access primary alcohols remains a significant synthetic challenge due to inherent regioselectivity constraints. Here we report a bio‐inspired iron catalyst bearing a cysteine‐derived ligand (BC <jats:italic>t</jats:italic> LOM) that enables radical hydroxyazidation of unconjugated tri‐, di‐, and monosubstituted alkenes with high anti‐Markovnikov selectivity. Utilizing TMSN <jats:sub>3</jats:sub> and hydrogen peroxide as azide source and oxidant, respectively, this method operates under mild conditions and tolerates diverse functional groups, including complex natural products and pharmaceuticals. Mechanistic studies suggest an iron‐oxo mediated radical pathway that suppresses competing epoxidation. This approach provides direct access to unprotected 2‐azido primary alcohols, versatile intermediates for further functionalization. The strategy expands the toolkit for selective alkene difunctionalization, offering potential applications in organic synthesis, chemical biology, and drug discovery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471515","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}
Paired electrolysis is being actively developed for co‐producing valuable chemicals by leveraging electron transfer at bipolar electrodes. In electrochemical CO 2 reduction to formate, if the reaction is coupled with oxygen evolution reaction, formate experiences severe crossover and oxidation to CO 2 over anode in membrane electrode assembly (MEA) electrolyzer. We reported a convergent electrolysis that produces formate at bipolar electrodes by coupling CO 2 reduction with biomass‐derived carbohydrate (for example, glucose) oxidation, maximizing the electron efficiency toward formate (0.88 formate per e − ) and suppressing oxidation of crossed formate at anode. This convergent electrolysis shows low electricity consumption for formate production (76.5 Wh mol −1 at 100 mA cm −2 ), lower than that of conventional CO 2 reduction (180−350 Wh mol −1 ). Furthermore, we extended the convergent electrolysis to acetate production by coupling electrochemical CO reduction with waste polylactic acid plastic oxidation. This work offers a framework for the rational design of paired electrolysis for low electricity consumption of chemical production.
{"title":"Electron‐Efficient Formate Electrosynthesis from CO 2 and Biomass‐Derived Carbohydrates in a Zero‐Gap Electrolyzer","authors":"Yue Ren, Ming Xu, Kang Zou, Wei Kong, Zhenhua Li, Xianggui Kong, Lirong Zheng, Zishan Han, Chunyu Zhang, Hua Zhou, Mingfei Shao, Haohong Duan","doi":"10.1002/anie.3951875","DOIUrl":"https://doi.org/10.1002/anie.3951875","url":null,"abstract":"Paired electrolysis is being actively developed for co‐producing valuable chemicals by leveraging electron transfer at bipolar electrodes. In electrochemical CO <jats:sub>2</jats:sub> reduction to formate, if the reaction is coupled with oxygen evolution reaction, formate experiences severe crossover and oxidation to CO <jats:sub>2</jats:sub> over anode in membrane electrode assembly (MEA) electrolyzer. We reported a convergent electrolysis that produces formate at bipolar electrodes by coupling CO <jats:sub>2</jats:sub> reduction with biomass‐derived carbohydrate (for example, glucose) oxidation, maximizing the electron efficiency toward formate (0.88 formate per e <jats:sup>−</jats:sup> ) and suppressing oxidation of crossed formate at anode. This convergent electrolysis shows low electricity consumption for formate production (76.5 Wh mol <jats:sup>−1</jats:sup> at 100 mA cm <jats:sup>−2</jats:sup> ), lower than that of conventional CO <jats:sub>2</jats:sub> reduction (180−350 Wh mol <jats:sup>−1</jats:sup> ). Furthermore, we extended the convergent electrolysis to acetate production by coupling electrochemical CO reduction with waste polylactic acid plastic oxidation. This work offers a framework for the rational design of paired electrolysis for low electricity consumption of chemical production.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"37 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471518","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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