Chemistry - A European Journal最新文献

{"title":"Iso-Tellurazole N-Oxides Assemble Adaptively Folded Macrocyclic Dodecamers.","authors":"Jin Z Wang, Phillip MacDougall, Mich W Zeng, James F Britten, Ignacio Vargas-Baca","doi":"10.1002/chem.71583","DOIUrl":"https://doi.org/10.1002/chem.71583","url":null,"abstract":"<p><p>Self-assembled macrocyclic dodecamers were found in the crystals of new pseudo-polymorphs of iso-tellurazole N-oxides. These structures are formed by molecules connected by NTe^…O chalcogen bonds and are folded in a pattern that defines 89-153 Å³ cavities, which are large enough to host solvent molecules. These crystals only grow in the presence of molecular species that can act as guests alone (cyclohexane) or in combination with sodium cations (1,4-dioxane, tetrahydrofuran, and pyrazine). A solution rich in a sodium salt yielded a crystal featuring a cage-like aggregate of three tetramers bridged by sodium cations, suggesting a plausible route for the formation of the new macrocycles by reorganization of the chalcogen bonds.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71583"},"PeriodicalIF":3.6,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Expanding the Scope of Indium in Frustrated Lewis Pair Chemistry.","authors":"Daniel N Heuer, Jan-Hendrik Lamm, Beate Neumann, Andreas Mix, Yury V Vishnevskiy, Norbert W Mitzel","doi":"10.1002/chem.71415","DOIUrl":"https://doi.org/10.1002/chem.71415","url":null,"abstract":"<p><p>The \"soft\" pyridine stabilized FLP ^tBu₂In(py)CH₂P^tBu₂ (1·py) was reacted with SO₂, PhNCO, PhNSO, azobenzene, pyridazine, 1,2,4,5-tetrazine, tosylaziridine, and hydrazine, respectively. The reactivity can be roughly classified into three types of FLP activation. (a) Typical FLP-type reactivity is observed for the reaction with azobenzene and tosylaziridine, with the formation of 1,2-addition or ring-opening products, respectively. (b) \"Soft\" FLP-type reactivity occurs toward substrates containing multiple sites for FLP attack-in this case 1·py prefers coordination to the \"softer\" binding site, resulting in the formation of \"soft\" isomers of possible FLP adducts, as was demonstrated for PhNCO and PhNSO. (c) An unexpected reactivity results that can be described as a \"masked\" In/C-FLP; when 1·py was reacted with SO₂, an insertion dimer formed, with the methylene bridge connected to the sulfur atom; the reaction of 1·py with hydrazine afforded a four-membered hydrazide heterocycle, under loss of the methylene bridge as MeP^tBu₂, instead of the reaction with the P^tBu₂ fragment, pyridine, or excess hydrazine. The products were characterized by a variety of NMR spectroscopy methods supported by X-ray crystallography as well as quantum-chemical calculations for insights into the thermodynamics and selectivity of product formation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71415"},"PeriodicalIF":3.6,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Compositional Stages in the Thermal Activation of Metal-Organic Frameworks in Vacuo: In Situ Spectroscopy and Computation.","authors":"George W Fritze, John W Robinson, Adam J Matzger","doi":"10.1002/chem.71633","DOIUrl":"https://doi.org/10.1002/chem.71633","url":null,"abstract":"<p><p>The final step in revealing the porosity of most metal-organic frameworks (MOFs), the ultimate step of the activation process, involves removal of solvent from the pores. This is commonly accomplished with the application of vacuum and heat; whereas some MOFs are readily activated under mild conditions, others must be heated to the point where decomposition can compete with activation. This latter class includes MOFs where the coordination of the metals to solvent must be disrupted for full activation. Here, the details of the solvent removal process are elucidated for two isostructural MOFs comprising divalent metals linked with 2,5-dioxidoterephthalate: Mg-MOF-74 and Zn-MOF-74. Using computational and spectroscopic data, structural and electronic changes undergone by the MOF are elucidated, providing insight into discrete intermediate states during the solvent removal process. Additionally, powder x-ray diffraction is analyzed to reveal features that are indicative of successful activation. These results provide a basis to design more efficient and effective MOF activation procedures.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71633"},"PeriodicalIF":3.6,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148878731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Twisted Benzothiazole Functionalized Boranils for Reversible Emission Modulation and Anthracene Assisted White Light Emission.","authors":"Pushpendra Singh, Menaka Chauhan, Abha Jha, Kalyan K Sadhu","doi":"10.1002/chem.71655","DOIUrl":"https://doi.org/10.1002/chem.71655","url":null,"abstract":"<p><p>Modification of boranils with dual state emissions in solution and solid states have been targeted by introducing free amine functional group at the terminal position. Herein, we designed and synthesized four new primary amine-substituted benzothiazole-based boranils from substituted salicylaldehyde. Their photophysical properties were investigated through steady-state absorption and emission measurements in both solution- and solid-states. X-ray structure analysis of the boranils revealed that the benzothiazole rings bearing the amine functional group are highly twisted, thereby avoiding the detrimental exciton interaction between the dimers and enabling emission in the solid state. In the solution-state, the naphthalene and methoxy substituted boranils exhibited significant intramolecular charge transfer and a large Stokes shift of > 150 nm. Julolidine or diethylamine substituted boranils exhibited reversible acid-base responsiveness via fluorescence ON-OFF properties. On the other hand, protonation and deprotonation of naphthalene and methoxy substituted boranils showed reversible blue and red shift emission. Computational studies revealed that the photo-induced electron transfer (PET) and photo-induced charge transfer (PICT) process were responsible for fluorescence enhancement and wavelength shift upon trifluoroacetic acid (TFA) treatment. Based on the solvent dependent wide emissive range, methoxy substituted boranil was further utilized for the generation of white light emission with anthracene as an ancillary component.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71655"},"PeriodicalIF":3.6,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148878769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"N-Boron-Functionalized Anionic N-Heterocyclic Carbenes (NBA-NHCs)-A Case Study.","authors":"Sophie Mann, Günther Horrer, Maik Finze, Udo Radius","doi":"10.1002/chem.71593","DOIUrl":"https://doi.org/10.1002/chem.71593","url":null,"abstract":"<p><p>The synthesis and characterization of a new family of N-boron-functionalized anionic NHCs (NBA-NHCs), IiPrB(CN)₃ ^- (5), IiPr(C₂F₅)BF₂ ^- (6), IMesB(CN)₃ ^- (7), and IMes(C₂F₅)BF₂ ^- (8), accessible on gram-scale from air- and moisture-stable precursors, is reported. Multinuclear NMR, IR spectroscopy, and single-crystal X-ray diffraction confirm highly electron-rich carbenic carbon centers and strengthened B-N interactions in these molecules. Selenium adducts 9-12 of these NBA-NHCs indicate an enhanced π-acceptor character relative to neutral NHCs, while Tolman electronic parameters of nickel tricarbonyl complexes [(NBA-NHC)Ni(CO)₃]^-K⁺ 13-16 demonstrate their strong donor ability, similar to dianionic carbenes. Steric maps and buried volume (%V_bur) analyses of linear gold(I) complexes [(NBA-NHC)Au(PPh₃)] 17-20 reveal tunable steric profiles, ranging from anisotropic to strongly shielding environments by varying the N-substituents. These results establish NBA-NHCs as a modular ligand platform enabling control of electronic properties and steric demand at the metal center for future applications in coordination chemistry and catalysis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71593"},"PeriodicalIF":3.6,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148878763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"GH172 Difructose Dianhydride I Synthase: A Two-Stepped Journey via Glycosylation and Cyclization Using QM/MM Metadynamics.","authors":"Santiago Alonso-Gil, Bruno Di Geronimo, Toma Kashima, Akihiro Ishiwata, Katsunori Tanaka, Kiyotaka Fujita, Shinya Fushinobu, Pedro A Sánchez-Murcia","doi":"10.1002/chem.71544","DOIUrl":"https://doi.org/10.1002/chem.71544","url":null,"abstract":"<p><p>The difructose dianhydride I synthase/hydrolase <math><mrow><mi>α</mi> <mrow><mi>FFase</mi> <mn>1</mn></mrow> </mrow> </math> catalyzes the reversible transformation of inulobiose into difructose dianhydride I, a component of caramel. The proposed reaction mechanism of such a transformation consists of a glycosylation step followed by a cyclization to yield the dianhydride from the disaccharide. Here, we make use of extensive hybrid QM/MM metadynamics studies to shed light on the molecular basis of it. Our simulations show that the global reaction for the transformation of inulobiose by <math><mrow><mi>α</mi> <mrow><mi>FFase</mi> <mn>1</mn></mrow> </mrow> </math> is slightly exergonic in good agreement with the experimental data. Furthermore, we observe that the glycosylation step is the rate-limiting step. Interestingly, our work shows that the -1 sugar of inulobiose changes from an initial E <math><msub><mrow></mrow> <mn>5</mn></msub> </math> conformation into a <math><msup><mrow></mrow> <mn>4</mn></msup> </math> E puckering via the conformational pathway E <math><msub><mrow></mrow> <mn>5</mn></msub> </math> <math><mo>→</mo></math> E <math><msub><mrow></mrow> <mn>5</mn></msub> </math> / <math><msup><mrow></mrow> <mn>4</mn></msup> </math> T <math><msub><mrow></mrow> <mn>5</mn></msub> </math> <math><mo>→</mo></math> E <math><msub><mrow></mrow> <mn>3</mn></msub> </math> <math><mo>→</mo></math> <math><msup><mrow></mrow> <mn>4</mn></msup> </math> E. Our calculations highlight that in the cyclization step, the three residues E85, K147, and N226 are essential for the rotation of the +1 sugar in the substrate to facilitate the intramolecular attack of oxygen O1' to the anomeric carbon. Prompted by these results, we expressed and assayed the N226A <math><mrow><mi>α</mi> <mrow><mi>FFase</mi> <mn>1</mn></mrow> </mrow> </math> variant. Enzyme activity data confirm an important role for N226 during the cyclization step but show that it is dispensable for the hydrolysis step.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71544"},"PeriodicalIF":3.6,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148872267","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Controlling Structures and Properties of NaCl-Containing Alginate/Polyacrylamide Tough Hydrogels via a One-Pot Process.","authors":"Taeuk Eom, Hyunseung Kim, Jihun Choi, Soon Joo Yoon, Yoon Kyeung Lee, Kwi-Il Park, Chang Kyu Jeong","doi":"10.1002/chem.71631","DOIUrl":"https://doi.org/10.1002/chem.71631","url":null,"abstract":"<p><p>Hydrogels have garnered significant interest as soft materials due to their flexibility, high water content, and biocompatibility. Alginate/polyacrylamide (Alg/PAAm) double-network (DN) hydrogels are particularly promising for wearable electronics, strain sensors, and soft electrolytes owing to their toughness and structural stability. However, the conventional soaking method for ion incorporation requires prolonged diffusion and often generates internal concentration gradients, leading to structural heterogeneity. This study introduces a one-pot strategy that incorporates NaCl directly into the precursor solution, enabling simultaneous gelation and ion integration. Elemental analyses indicate a more spatially consistent Na and Cl distribution across the examined surface regions of the one-pot hydrogel compared with the soaking-derived hydrogel. Furthermore, NaCl incorporation influences network formation primarily by modifying the ionic environment and hydration state rather than by creating new covalent bonds. The resulting hydrogels exhibit a composition-dependent trade-off between mechanical reinforcement and ionic transport. NaCl concentrations of 1.5-2.0 wt% provide a favorable balance among stiffness, strength, and deformability, whereas ionic conductivity reaches its maximum at 12.5 wt%. These findings indicate that no single NaCl concentration is optimal for all performance requirements and that the salt content should instead be tailored to the intended application.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71631"},"PeriodicalIF":3.6,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148878750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"N-Aryl Acridone Derivatives as Effective Catalysts for Energy Transfer Reactions.","authors":"Francesco Calogero, Gaetano D'Onghia, Federica Fina, Zakaria Ziani, Luca Sensoli, Andrea Gualandi, Andrea Fermi, Paola Ceroni, Pier Giorgio Cozzi","doi":"10.1002/chem.71143","DOIUrl":"10.1002/chem.71143","url":null,"abstract":"<p><p>Organic photocatalysts capable of promoting high-energy triplet energy transfer (EnT) remain limited, particularly for demanding [2+2] photocycloaddition reactions. In this study, we report the use of readily accessible N-aryl acridones as efficient visible-light-driven organic photocatalysts for challenging EnT processes. Although largely unexplored in photocatalysis, acridone derivatives exhibit photophysical properties suitable for sensitizing substrates with high triplet energies. Using N-Boc-indole-2-methyl ester and coumarin as representative high-triplet-energy substrates, we demonstrate that N-aryl acridones effectively mediate [2+2] cycloadditions under mild conditions via an energy-transfer mechanism. The modular acridone scaffold enables straightforward structural modification through N-functionalization, allowing systematic tuning of electronic and steric parameters to optimize catalytic performance.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71143"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532161/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147979811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improvements in the Total Synthesis of Ruxolitinib Through Mechanochemistry, Microwave Irradiation, and Green Solvents.","authors":"Zuzana Mravíková, Tibor Peňaška, Kveta Vargová, Radovan Šebesta","doi":"10.1002/chem.71650","DOIUrl":"https://doi.org/10.1002/chem.71650","url":null,"abstract":"<p><p>Syntheses of highly structurally complex compounds such as pharmaceuticals belong among the most demanding from a sustainability point of view. Herein, we present the total synthesis of an important pharmaceutical, ruxolitinib, through the strategic application of mechanochemistry, microwave irradiation, and green solvents. Mechanochemistry proved useful for the Wittig reaction, ester reduction, and alcohol oxidation, leading to short reaction times and high yields. Moreover, the key step of the synthesis, the asymmetric organocatalytic aza-Michael addition, can also be carried out under mechanochemical conditions, affording an aza-Michael adduct with high enantiomeric purity. Alternatively, this step can be augmented by using green solvent alternatives. Final functional group transformation and deprotection benefited from microwave irradiation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71650"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148862591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamic Olefinic Bond Restructuring in Coordination Polymers Enables Precision Photocycloaddition","authors":"Qiaoqiao Zhang,&nbsp;Yong Wang,&nbsp;Xin-Yi Huang,&nbsp;Shuai Yuan,&nbsp;Jian-Ping Lang","doi":"10.1002/chem.202502830","DOIUrl":"10.1002/chem.202502830","url":null,"abstract":"<div>\u0000 \u0000 <p>Biological systems adapt their conformations and reactivities in response to diverse external cues, inspiring the development of synthetic materials with similar responsiveness for controlled chemical transformations. Here we report a flexible coordination polymer, [{Cd₄(OCH₃-BPEB)₄(OBA)₄}·7DEF]_n (<b>CP1</b>, OCH₃-BPEB = 4,4'-((1<i>E</i>,1'<i>E</i>)-(2,5-dimethoxyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine, H₂OBA = 4,4'-oxybis(benzoic acid), DEF = <i>N</i>,<i>N</i>-diethylformamide), capable of multistimuli-induced restructuring of otherwise inactive olefinic bond pairs to achieve regioselective [2+2] photocycloadditions. Sequence exposure to solvent vapours and visible light drives stepwise structural transformations, producing two monocyclobutane isomers—4,4'-((1<i>S</i>,3<i>R</i>)bis(2,5-dimethoxyl-4-((<i>E</i>)-2-(pyridin-4-yl)vinyl)phenyl)cyclobutane-1,2-diyl)dipyridine (OCH₃-PCDP) and 4,4'-((1<i>R</i>,2<i>R</i>,3<i>S</i>,4<i>S</i>)-2,4-bis(2,5-dimethoxy-4-((<i>E</i>)-2-(pyridin-4-yl)vinyl)phenyl)cyclobutane-1,3-diyl)dipyridine, (2,4-OCH₃-PCDP)—from their respective photoirradiated derivatives [{Cd₄(OCH₃-PCDP)₂(OBA)₄}·3DEF]_n (<b>CP2</b>) and [{Cd₄(2,4-OCH₃-PCDP)₂(OBA)₄}·3MeOH]_n (<b>CP3</b>, MeOH = methanol). Single-crystal X-ray diffraction captures five intermediate structures, and density functional theory (DFT) calculations elucidate how stimuli-mediated realignment of olefinic pairs dictates regioselectivity. This work demonstrates precise photochemical cyclobutane synthesis within a coordination polymer single-crystal platform, offering mechanistic insights applicable to the broader design of stimuli-controlled photoreactions and functional materials.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 33","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}