The Diels-Alder reaction is a cornerstone of organic synthesis, enabling construction of complex molecular architectures through the cycloaddition of dienes and dienophiles. Among dienes, ortho-quinodimethane is an exceptionally powerful intermediate for building benzo-fused polycyclic skeletons found in biologically important molecules. However, the requirement for laborious precursor preparation remains a significant challenge. This study presents a palladium-catalyzed generation of ortho-quinodimethane via a multi-component reaction of readily available chemicals, specifically 2-vinylbromoarenes, diazo species, and carbon nucleophiles bearing a dienophile moiety, yielding polycyclic compounds. A key advance is the unprecedented reactivity of a benzyl-palladium intermediate, enabling C–C bond formation on the vinyl group. The convergent and diversity-generating nature of this reaction is demonstrated by the synthesis of a range of polycyclic compounds, including a natural product.
{"title":"Facile generation of ortho-quinodimethanes toward polycyclic compounds","authors":"Kazuya Inagaki , Yuna Onozawa , Yuki Fukuhara , Daisuke Yokogawa , Kei Muto , Junichiro Yamaguchi","doi":"10.1016/j.chempr.2025.102615","DOIUrl":"10.1016/j.chempr.2025.102615","url":null,"abstract":"<div><div>The Diels-Alder reaction is a cornerstone of organic synthesis, enabling construction of complex molecular architectures through the cycloaddition of dienes and dienophiles. Among dienes, <em>ortho</em>-quinodimethane is an exceptionally powerful intermediate for building benzo-fused polycyclic skeletons found in biologically important molecules. However, the requirement for laborious precursor preparation remains a significant challenge. This study presents a palladium-catalyzed generation of <em>ortho</em>-quinodimethane via a multi-component reaction of readily available chemicals, specifically 2-vinylbromoarenes, diazo species, and carbon nucleophiles bearing a dienophile moiety, yielding polycyclic compounds. A key advance is the unprecedented reactivity of a benzyl-palladium intermediate, enabling C–C bond formation on the vinyl group. The convergent and diversity-generating nature of this reaction is demonstrated by the synthesis of a range of polycyclic compounds, including a natural product.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102615"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192762","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102625
Beomsoon Park , Kyoungil Cho , Kyungmin Choi , Soon Hyeok Hong
Despite the invaluable properties and broad applications of synthetic elastomers, the management of waste rubbers and end-of-life tires typically involves mechanical recycling or conversion into low-grade fuel. This study introduces an effective and selective chemical recycling method for synthetic elastomers, including polybutadiene, polycycloalkenamers, and their copolymers, utilizing a synergistic tandem catalysis approach that combines isomerization and ring-closing metathesis. By exploiting the ring-chain equilibrium of oligomers, we have demonstrated the selective depolymerization of rubbers into C5–C7 cycloalkenes. Importantly, this method effectively depolymerizes post-consumer vulcanized rubbers, such as disposable rubbers and tires, converting them into highly valuable chemical feedstocks. These results highlight the significant potential of tandem dual catalysis for the selective chemical recycling of synthetic rubbers.
{"title":"Catalytic and selective chemical recycling of post-consumer rubbers into cycloalkenes","authors":"Beomsoon Park , Kyoungil Cho , Kyungmin Choi , Soon Hyeok Hong","doi":"10.1016/j.chempr.2025.102625","DOIUrl":"10.1016/j.chempr.2025.102625","url":null,"abstract":"<div><div>Despite the invaluable properties and broad applications of synthetic elastomers, the management of waste rubbers and end-of-life tires typically involves mechanical recycling or conversion into low-grade fuel. This study introduces an effective and selective chemical recycling method for synthetic elastomers, including polybutadiene, polycycloalkenamers, and their copolymers, utilizing a synergistic tandem catalysis approach that combines isomerization and ring-closing metathesis. By exploiting the ring-chain equilibrium of oligomers, we have demonstrated the selective depolymerization of rubbers into C<sub>5</sub>–C<sub>7</sub> cycloalkenes. Importantly, this method effectively depolymerizes post-consumer vulcanized rubbers, such as disposable rubbers and tires, converting them into highly valuable chemical feedstocks. These results highlight the significant potential of tandem dual catalysis for the selective chemical recycling of synthetic rubbers.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102625"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312134","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102617
Osama El-Zubir , James A. Quirk , James A. Dawson , Benjamin R. Horrocks , Andrew Houlton
Biology’s information carrier, DNA, through its reliable synthesis, controllable length, and sequence-coded self-assembly, provides a unique capability for molecular-material/-device design. However, the intrinsic lack of tunable optoelectronics associated, generally, with delocalized electronic structures means it commonly acts in a passive role to organize “functional” components. The introduction of metal ions into duplex DNA to overcome this limitation has been widely explored, but, to date, the demonstration of such electronically delocalized motifs has proved elusive. Here, we incorporate Au(I)-thionate coordination chains into discrete duplex-DNA molecules by substituting native guanosine with the sulfur-modified analog, 6-thioguanosine. The resulting “24-karat DNA” displays the associated photoluminescence of the metallo chain, along with chiro-optical properties indicating this is conformationally flexible, adopting a duplex-matching helical arrangement. Furthermore, due to the electronic delocalization in the coordination chain, these features can be modulated by a simple extension of the thioG-sequence and {μS-Au-}n chain length and so provide a new tunability to the electronic structure of DNA-based architectures.
{"title":"24-karat DNA: Integrating tunable electronically delocalized coordination chains into discrete DNA duplexes","authors":"Osama El-Zubir , James A. Quirk , James A. Dawson , Benjamin R. Horrocks , Andrew Houlton","doi":"10.1016/j.chempr.2025.102617","DOIUrl":"10.1016/j.chempr.2025.102617","url":null,"abstract":"<div><div>Biology’s information carrier, DNA, through its reliable synthesis, controllable length, and sequence-coded self-assembly, provides a unique capability for molecular-material/-device design. However, the intrinsic lack of tunable optoelectronics associated, generally, with delocalized electronic structures means it commonly acts in a passive role to organize “functional” components. The introduction of metal ions into duplex DNA to overcome this limitation has been widely explored, but, to date, the demonstration of such electronically delocalized motifs has proved elusive. Here, we incorporate Au(I)-thionate coordination chains into discrete duplex-DNA molecules by substituting native guanosine with the sulfur-modified analog, 6-thioguanosine. The resulting “24-karat DNA” displays the associated photoluminescence of the metallo chain, along with chiro-optical properties indicating this is conformationally flexible, adopting a duplex-matching helical arrangement. Furthermore, due to the electronic delocalization in the coordination chain, these features can be modulated by a simple extension of the thioG-sequence and {μS-Au-}<sub>n</sub> chain length and so provide a new tunability to the electronic structure of DNA-based architectures.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102617"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202217","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102664
Ryo Tanifuji , Erina Hosono , Hisae Kamakura , Yukiko Muramatsu , Satoshi Yoshida , Sota Sato , Yoshimi Ohashi , Shingo Dan , Hiroyuki Seimiya , Hiroki Oguri
Strategies for rational design and scaffold diversification of therapeutically valuable yet synthetically challenging natural products remain elusive, often overshadowed by structural simplification approaches. Herein, we report the molecular redesign of an antitumor drug, ecteinascidin 743, which achieves three pivotal objectives: (1) strategic shift of the bridgehead position from C4 to C5, (2) systematic customization of macrocycle size, and (3) incorporation of functional groups for further modification. Our approach generates diverse 14- to 17-membered macrocyclic frameworks bridged at C5, expanding the accessible chemical space beyond that of conventional C1- to C4-bridged scaffolds, while preserving the core structure essential for covalent DNA interactions. These novel macrocycles induce DNA double-strand breaks and exhibit sub-nanomolar anticancer efficacy comparable to ecteinascidins. This method shortens the conventional 21-step semi-synthetic protocol into a streamlined 6- to 10-step process, cutting the synthetic burden by over 50%.
{"title":"Strategic scaffold redesign of ecteinascidins: An approach for generating anticancer macrocycles","authors":"Ryo Tanifuji , Erina Hosono , Hisae Kamakura , Yukiko Muramatsu , Satoshi Yoshida , Sota Sato , Yoshimi Ohashi , Shingo Dan , Hiroyuki Seimiya , Hiroki Oguri","doi":"10.1016/j.chempr.2025.102664","DOIUrl":"10.1016/j.chempr.2025.102664","url":null,"abstract":"<div><div>Strategies for rational design and scaffold diversification of therapeutically valuable yet synthetically challenging natural products remain elusive, often overshadowed by structural simplification approaches. Herein, we report the molecular redesign of an antitumor drug, ecteinascidin 743, which achieves three pivotal objectives: (1) strategic shift of the bridgehead position from C4 to C5, (2) systematic customization of macrocycle size, and (3) incorporation of functional groups for further modification. Our approach generates diverse 14- to 17-membered macrocyclic frameworks bridged at C5, expanding the accessible chemical space beyond that of conventional C1- to C4-bridged scaffolds, while preserving the core structure essential for covalent DNA interactions. These novel macrocycles induce DNA double-strand breaks and exhibit sub-nanomolar anticancer efficacy comparable to ecteinascidins. This method shortens the conventional 21-step semi-synthetic protocol into a streamlined 6- to 10-step process, cutting the synthetic burden by over 50%.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102664"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652626","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102758
Asmaa Jrad , Bikash Garai , Samer Aouad , Gobinda Das , Connor M. Duncan , Mark A. Olson , Ali Trabolsi
Per- and polyfluoroalkyl substances (PFAS), known as “forever chemicals,” are persistent pollutants with serious environmental and health impacts. Conventional water treatment methods often fall short of removing PFAS, prompting interest in advanced adsorbents such as covalent organic frameworks (COFs). This review explores recent advances in the development of COFs tailored for PFAS removal. The discussion focuses on key adsorption mechanisms, including hydrophobic, fluorophilic, electrostatic, and hydrogen-bonding interactions. In addition, optimizing pore size and particle size to improve the adsorption of PFAS is highlighted. The potential of COFs for practical applications is evaluated through their integration into composites, membranes, and adsorption columns, which enable continuous flow treatment. Despite promising results, challenges remain, including scalability, synthesis complexity, and realistic testing at environmentally relevant PFAS concentrations. The outline of future research directions aims to drive the advancement of COF-based solutions that have the potential to revolutionize PFAS remediation in real-world applications.
{"title":"Redefining forever: Advancements, challenges, and opportunities in covalent organic frameworks for the remediation of forever chemicals","authors":"Asmaa Jrad , Bikash Garai , Samer Aouad , Gobinda Das , Connor M. Duncan , Mark A. Olson , Ali Trabolsi","doi":"10.1016/j.chempr.2025.102758","DOIUrl":"10.1016/j.chempr.2025.102758","url":null,"abstract":"<div><div>Per- and polyfluoroalkyl substances (PFAS), known as “forever chemicals,” are persistent pollutants with serious environmental and health impacts. Conventional water treatment methods often fall short of removing PFAS, prompting interest in advanced adsorbents such as covalent organic frameworks (COFs). This review explores recent advances in the development of COFs tailored for PFAS removal. The discussion focuses on key adsorption mechanisms, including hydrophobic, fluorophilic, electrostatic, and hydrogen-bonding interactions. In addition, optimizing pore size and particle size to improve the adsorption of PFAS is highlighted. The potential of COFs for practical applications is evaluated through their integration into composites, membranes, and adsorption columns, which enable continuous flow treatment. Despite promising results, challenges remain, including scalability, synthesis complexity, and realistic testing at environmentally relevant PFAS concentrations. The outline of future research directions aims to drive the advancement of COF-based solutions that have the potential to revolutionize PFAS remediation in real-world applications.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102758"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241672","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102782
Xue Chen , Yang Liu , Qing-Hui Guo
Stabilizing and characterizing cyclocarbons are a significant challenge in carbon materials science. In the August 14 issue of Science, Anderson and Gao employ a dynamic protection strategy to achieve the stable existence and comprehensive spectroscopic characterization of cyclo[48]carbon in ambient solution. This latest breakthrough will pave the way for uncovering new carbon allotropes.
{"title":"Catenated cyclocarbon: Stabilizing cyclo[48]carbon in solution with mechanical bonds","authors":"Xue Chen , Yang Liu , Qing-Hui Guo","doi":"10.1016/j.chempr.2025.102782","DOIUrl":"10.1016/j.chempr.2025.102782","url":null,"abstract":"<div><div>Stabilizing and characterizing cyclocarbons are a significant challenge in carbon materials science. In the August 14 issue of <em>Science</em>, Anderson and Gao employ a dynamic protection strategy to achieve the stable existence and comprehensive spectroscopic characterization of cyclo[48]carbon in ambient solution. This latest breakthrough will pave the way for uncovering new carbon allotropes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102782"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247336","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102616
Shinji Aoyama , Lorenzo Catti , Michito Yoshizawa
Porous aromatic/polyaromatic polymers (PAPs) have been widely investigated as polycavity materials, featuring infinite grid frameworks with high stability. However, in contrast to host-guest functions in mono/oligocavities, the applications of these polycavities remained largely limited, owing to the complete insolubility, ill-defined structures, and inseparability. Here, we report a general strategy for the facile preparation of aqueous polycavity hosts through uptake of insoluble PAPs within aromatic micelles in water. The obtained aqueous host-guest composites, e.g., including a pyrene-benzene-based PAP, are analyzed via solution/solid-state techniques, revealing roughly spherical ∼100 nm-sized particles. The giant composites can be easily size fractionated in a highly monodisperse fashion using a centrifugation-filtration protocol. Importantly, the water-soluble polycavities of the PAPs within the micelle provide cavity-dependent incorporation abilities toward hydrocarbons, accompanying large emission enhancement (up to ∼9-fold) of the semi-rigid polycavities. Medium-sized dyes and hydrocarbons are furthermore co-incorporated into the polycavities, yielding unusual quaternary host-guest composites with enhanced dye-based emission.
{"title":"Aqueous polycavity hosts composed of porous aromatic polymers within aromatic micelles","authors":"Shinji Aoyama , Lorenzo Catti , Michito Yoshizawa","doi":"10.1016/j.chempr.2025.102616","DOIUrl":"10.1016/j.chempr.2025.102616","url":null,"abstract":"<div><div>Porous aromatic/polyaromatic polymers (PAPs) have been widely investigated as polycavity materials, featuring infinite grid frameworks with high stability. However, in contrast to host-guest functions in mono/oligocavities, the applications of these polycavities remained largely limited, owing to the complete insolubility, ill-defined structures, and inseparability. Here, we report a general strategy for the facile preparation of aqueous polycavity hosts through uptake of insoluble PAPs within aromatic micelles in water. The obtained aqueous host-guest composites, e.g., including a pyrene-benzene-based PAP, are analyzed via solution/solid-state techniques, revealing roughly spherical ∼100 nm-sized particles. The giant composites can be easily size fractionated in a highly monodisperse fashion using a centrifugation-filtration protocol. Importantly, the water-soluble polycavities of the PAPs within the micelle provide cavity-dependent incorporation abilities toward hydrocarbons, accompanying large emission enhancement (up to ∼9-fold) of the semi-rigid polycavities. Medium-sized dyes and hydrocarbons are furthermore co-incorporated into the polycavities, yielding unusual quaternary host-guest composites with enhanced dye-based emission.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102616"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192764","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102597
Dihao Wang , Dvir Harris , Chern Chuang , Graham P. Schmidt , Olivia C. Fiebig , Gabriela S. Schlau-Cohen
Purple bacteria convert solar energy into biochemical energy with high quantum efficiency across diverse environments. Under low light, many species increase the number of antenna complexes and replace their primary light-harvesting complex 2 (LH2) with a blue-shifted variant, LH3. The structural basis of the blue shift and its influence on the dynamics of solar energy conversion have remained unclear. Here, we integrated cryogenic electron microscopy, ultrafast spectroscopy, and quantum dynamics simulations to compare LH2 and LH3 from Rhodoblastus acidophilus strain 7750. Our analyses revealed that hydrogen bonding dynamically tunes the transition energy, introducing a previously unreported excitation energy equilibrium between bacteriochlorophyll rings in LH3. This energy redistribution opened new inter-complex pathways, enabling 68% faster energy transport to maintain high conversion efficiency even with the larger antenna. Collectively, these results establish structural modifications as a tunable knob to optimize both absorption and transport for robust light harvesting under fluctuating conditions.
{"title":"Robust light-harvesting properties upon low-light acclimation in purple bacteria","authors":"Dihao Wang , Dvir Harris , Chern Chuang , Graham P. Schmidt , Olivia C. Fiebig , Gabriela S. Schlau-Cohen","doi":"10.1016/j.chempr.2025.102597","DOIUrl":"10.1016/j.chempr.2025.102597","url":null,"abstract":"<div><div>Purple bacteria convert solar energy into biochemical energy with high quantum efficiency across diverse environments. Under low light, many species increase the number of antenna complexes and replace their primary light-harvesting complex 2 (LH2) with a blue-shifted variant, LH3. The structural basis of the blue shift and its influence on the dynamics of solar energy conversion have remained unclear. Here, we integrated cryogenic electron microscopy, ultrafast spectroscopy, and quantum dynamics simulations to compare LH2 and LH3 from <em>Rhodoblastus acidophilus</em> strain 7750. Our analyses revealed that hydrogen bonding dynamically tunes the transition energy, introducing a previously unreported excitation energy equilibrium between bacteriochlorophyll rings in LH3. This energy redistribution opened new inter-complex pathways, enabling 68% faster energy transport to maintain high conversion efficiency even with the larger antenna. Collectively, these results establish structural modifications as a tunable knob to optimize both absorption and transport for robust light harvesting under fluctuating conditions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102597"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154179","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102619
Till Schertenleib , Mehrdad Asgari , Beatriz Mouriño , Vikram V. Karve , Timo M.O. Felder , Dragos Stoian , Volodymyr Bon , Jian Hao , Andres Ortega-Guerrero , Emad Oveisi , Kumar Varoon Agrawal , Berend Smit , Stefan Kaskel , Simon J.L. Billinge , Wendy L. Queen
We introduce a new approach to defect engineering in Zr-based metal-organic frameworks (Zr-MOFs), aiming to reduce Zr site valency while preserving high node connectivity. Using a rapid heat treatment (RHT) in humid air, oxygen vacancies (O-vacancies) were created in Dresden University of Technology (DUT)-67 through cluster dehydration. Unlike conventional defect engineering, aimed at creating missing-linker defects, this method breaks intra-cluster Zr-O–Zr bonds, generating coordinatively unsaturated Zr (Zrcus) sites. Pair distribution function (PDF) analysis, X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations reveal that the O-vacancies lead to symmetry breaking, irreversible node distortions, and framework amorphization. This treatment converts 50% of metal sites to Zrcus sites, nearly doubling the catalytic activity of DUT-67 in glyoxal conversion to glycolic acid. DFT modeling and in situ PDF analysis highlight the dynamic behavior of Zr clusters under reaction conditions, suggesting a new avenue for defect engineering in Zr-MOFs to enhance catalytic performance.
{"title":"Anisotropic node distortions in amorphous MOFs: Low-valent Zr sites as catalytic hotspots","authors":"Till Schertenleib , Mehrdad Asgari , Beatriz Mouriño , Vikram V. Karve , Timo M.O. Felder , Dragos Stoian , Volodymyr Bon , Jian Hao , Andres Ortega-Guerrero , Emad Oveisi , Kumar Varoon Agrawal , Berend Smit , Stefan Kaskel , Simon J.L. Billinge , Wendy L. Queen","doi":"10.1016/j.chempr.2025.102619","DOIUrl":"10.1016/j.chempr.2025.102619","url":null,"abstract":"<div><div>We introduce a new approach to defect engineering in Zr-based metal-organic frameworks (Zr-MOFs), aiming to reduce Zr site valency while preserving high node connectivity. Using a rapid heat treatment (RHT) in humid air, oxygen vacancies (O-vacancies) were created in Dresden University of Technology (DUT)-67 through cluster dehydration. Unlike conventional defect engineering, aimed at creating missing-linker defects, this method breaks intra-cluster Zr-<span><math><mrow><msub><mi>μ</mi><mn>3</mn></msub></mrow></math></span>O–Zr bonds, generating coordinatively unsaturated Zr (Zr<sub>cus</sub>) sites. Pair distribution function (PDF) analysis, X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations reveal that the O-vacancies lead to symmetry breaking, irreversible node distortions, and framework amorphization. This treatment converts 50% of metal sites to Zr<sub>cus</sub> sites, nearly doubling the catalytic activity of DUT-67 in glyoxal conversion to glycolic acid. DFT modeling and <em>in situ</em> PDF analysis highlight the dynamic behavior of Zr clusters under reaction conditions, suggesting a new avenue for defect engineering in Zr-MOFs to enhance catalytic performance.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102619"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269103","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}
{"title":"Manipulation of intramolecular charge transfer in NIR-II emissive organic diradicaloids via a symmetry-breaking design","authors":"Tingting Huang, Kun Yang, Wei Hu, Lina Feng, Zipeng Wu, Hui Chen, Jianguo Wang, Zebing Zeng","doi":"10.1016/j.chempr.2025.102659","DOIUrl":"10.1016/j.chempr.2025.102659","url":null,"abstract":"","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102659"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516288","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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