Journal of the American Chemical Society最新文献

{"title":"Synthesis of Electron-Deficient BisAzaCoroneneDiimide-Conjugated Polymers by Light-Locking Dynamic Covalent Bonds","authors":"Adèle Gapin, Elarbi Chatir, Olivier Alévêque, Clara Pasgrimaud, Arthur H. G. David, Anaïs De Maria, Mélanie Legros, Laura Le Bras, Eric Levillain, Antoine Goujon","doi":"10.1021/jacs.5c01351","DOIUrl":"https://doi.org/10.1021/jacs.5c01351","url":null,"abstract":"We present a novel light-locked dynamic covalent polymerization methodology to synthesize conjugated polymers based on BisAzaCoroneneDiimides (BACDs). This metal-free process converts reversible poly imines into kinetically locked conjugated polymers using visible light, generating minimal side products. By incorporating aldehyde-functionalized comonomers, the approach enables the creation of diverse n-type semiconducting polymers with tunable optical band gaps and low LUMO levels. The polymers exhibit exceptional thermal, electrochemical, and photostability with strong interchain interactions upon electrochemical reduction observed in solution, attributed to the BACD core. Broad absorption from the visible to the near-infrared range underscores their potential in charge and energy transport applications for organic electronics. This scalable, sustainable strategy unlocks access to a versatile class of n-type diimide polymers.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"66 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734368","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":"Reactivating Molecular Cobalt Catalysts for Electrochemical CO2 Conversion to Methanol","authors":"Sunmoon Yu, Hiroki Yamauchi, Davide Menga, Shuo Wang, Antonia Herzog, Hongbin Xu, Daniel J. Zheng, Xiao Wang, Haldrian Iriawan, Botao Huang, Alexander Nitsche, Yang Shao-Horn","doi":"10.1021/jacs.5c02411","DOIUrl":"https://doi.org/10.1021/jacs.5c02411","url":null,"abstract":"Molecular catalysts immobilized on a carbon support have demonstrated electrocatalytic CO₂ conversion capabilities distinct from those of metallic surfaces. For instance, cobalt phthalocyanine supported on carbon nanotubes (CoPc/CNT) is capable of selective CO₂-to-methanol conversion with ∼30% selectivity, which cannot be accomplished by other metal catalysts, such as cobalt, silver, and copper. However, despite its promising methanol selectivity, the CoPc/CNT catalyst exhibits a gradual decrease in the methanol production rate during the electrochemical CO₂ reduction reaction (CO₂RR). This catalytic instability impedes its practical application, yet little is known about the origin of the activity decay and viable solutions to circumvent it. In this study, we show that the catalytic deactivation is not an irreversible process caused by the chemical degradation of the catalyst and present reactivation strategies to recover the catalytic performance for stable methanol production. We propose that formaldehyde, an intermediate generated during the CO₂RR, can act as a poisoning species, and its adsorption configuration on the cobalt site can determine the fate of its reaction pathway: carbon-down (*CH₂O) versus oxygen-down (*OCH₂) pathways. In contrast to the carbon-down configuration leading to methanol production, the oxygen-down configuration can inhibit its further reduction, poisoning the cobalt active site and causing the deactivation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"662 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734369","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":"Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites","authors":"Yong Yuan, Tianyou Mou, Sooyeon Hwang, William N. Porter, Ping Liu, Jingguang G. Chen","doi":"10.1021/jacs.5c01105","DOIUrl":"https://doi.org/10.1021/jacs.5c01105","url":null,"abstract":"Designing efficient ligand-free heterogeneous catalysts for ethylene hydroformylation to produce C₃ oxygenates is of importance for both fundamental research and practical applications, but it is often hindered by insufficient catalytic activity and selectivity. This work designs isolated rhodium–cobalt (Rh–Co) sites confined within a ZSM-5 zeolite to enhance ethylene hydroformylation rates and selectivity while maintaining catalyst stability. By adjusting the Co/Al ratio in Co-ZSM-5, different sizes of Co are formed; subsequent Rh introduction produces isolated Rh₁Co<i>_<i>x</i></i> clusters with different Rh–Co coordination numbers (CNs). In-situ characterizations and density functional theory calculations reveal that a Rh–Co CN of 3, corresponding to an isolated Rh₁Co₃ site, provides optimal bindings to reaction intermediates and thus achieves the highest hydroformylation rates among supported Rh-based catalysts. This study demonstrates the role of coordination-tuning via a secondary metal in effectively controlling the reaction pathway over single Rh atom catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734367","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":"Titanium Phosphinidene and Phosphide Moieties from Oxidative Phosphorylation and Desilylation","authors":"Jacob S. Mohar, Mrinal Bhunia, Alexander L. Laughlin, Andrew Ozarowski, J. Krzystek, Taylor M. Keller, Michael R. Gau, Kyle M. Lancaster, Joshua Telser, Daniel J. Mindiola","doi":"10.1021/jacs.4c12242","DOIUrl":"https://doi.org/10.1021/jacs.4c12242","url":null,"abstract":"A unique entry into mononuclear titanium complexes bearing phosphinidene and phosphide ligand moieties is reported. Reaction of [K(crypt)][(PN)₂TiCl] (<b>1</b>, crypt = 2.2.2-cryptand) with [Na(OCP)] results in [K(crypt)][(PN)₂Ti(OCP)] (<b>2</b>) and such species can be oxidized to the derivative [(PN)₂Ti(OCP)] (<b>3</b>), both of which do not undergo decarbonylation. However, the reaction of <b>1</b> and [NaP(SiMe₃)₂] leads to an unprecedented Ti^III phosphinidene, [K(crypt)][(PN)₂Ti═PSiMe₃] (<b>4</b>), through an oxidative phosphorylation reaction. To promote the formation of a Ti≡P bond, complex <b>4</b> was treated with 0.5 equivalent XeF₂, resulting in an oxidative desilylation step forming a molecular titanium phosphide complex, [K(crypt)][(PN)₂Ti≡P] (<b>5</b>), which showed a characteristic downfield chemical shift at 1449.8 pmm in the ³¹P NMR spectrum. Complex <b>5</b> can be further functionalized to generate a terminal Ti^IV phosphinidene, [(PN)₂Ti═PSiMe₃] (<b>6</b>), and the latter can be independently accessed through oxidation of <b>4</b>. All new complexes were characterized structurally and as appropriate by multinuclear NMR, CW X-band EPR (for Ti^III), and HFEPR (for Ti^II) spectroscopies.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"100 5 Pt 1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723939","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":"Correction to “Discovery of a Natural Ent-Kaurene Diterpenoid Oridonin as an E3 Ligase Recruiter for PROTACs”","authors":"Jie Huang, Xuekun Fu, Fang Qiu, Zhijian Liang, Chunhao Cao, Zhuqian Wang, Hongzhen Chen, Siran Yue, Duoli Xie, Yiying Liang, Aiping Lu, Chao Liang","doi":"10.1021/jacs.5c03656","DOIUrl":"https://doi.org/10.1021/jacs.5c03656","url":null,"abstract":"In Figure S6E, the band of TUBULIN was incorrect. The revised Supporting Information file provided here shows the correct band. This change does not alter the conclusions of the published work. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c03656. Materials and Methods; Figures S1–S14; Tables S1–S2; and Supporting Notes 1–11 (PDF) Correction to “Discovery\u0000of a Natural Ent-Kaurene\u0000Diterpenoid Oridonin as an E3 Ligase Recruiter for PROTACs” <span> 1 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723852","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":"Solvent Medium-Induced Changes to Internal Pressure in the Layered Host VOPO4·2H2O and the Influence on Intercalation Reactions","authors":"Jiahui Liu, Yuan Liu, Timothy Yoo, Miho Itoi, Honggyu Kim, Simon R. Phillpot, Daniel R. Talham","doi":"10.1021/jacs.4c16643","DOIUrl":"https://doi.org/10.1021/jacs.4c16643","url":null,"abstract":"Layered vanadium phosphate dihydrate, VOPO₄·2H₂O, has been chosen as a host for ferrocene intercalation to explore the influence of solvent-guest and solvent-host interactions on rates and product selection. After eliminating solvents that react directly with the VOPO₄·2H₂O host, ferrocene intercalation was evaluated in a series of seven solvents that do not themselves intercalate or otherwise alter the host structure. The intercalation kinetics are analyzed in acetone, butanone, pentanone, acetonitrile, propionitrile, butyronitrile, and DMF. No intercalation is observed in DMF, but all other solvents yield a mixture of stage 1 and stage 2 ferrocenium intercalation products with reaction rates and product ratios varying across the series of solvents. Using <i>ex situ</i> as well as <i>in situ</i> PXRD methods, faster reactions yield more stage 1 product, while a higher degree of stage 2 product is seen for slower kinetics. The results are interpreted in the context of competition between intercalation rates and the buildup of elastic strain between intercalated domains and unintercalated host. To understand solvent effects, both solvent-guest and solvent-host effects are considered. None of the typically considered solvent-guest effects, such as guest desolvation energy, dielectric constant, and guest oxidation potential, correlate with the observed reaction kinetics. On the other hand, different solvent environments are shown to change the internal pressure, <i>P</i>_eff, within the layered hosts, a consequence of changing surface energy and surface tension (stress) in particles with nanometer scale dimensions. The VOPO₄·2H₂O interlayer spacing decreases when particles are suspended in DMF and organonitrile solvents, while the layers separate slightly in acetone, butanone, and pentanone. Using calculated elastic constants, the structural changes correspond to changes in <i>P</i>_eff in the range 0.22 GPa &gt; Δ<i>P</i>_eff &gt; −0.11 GPa across the series of solvents. A density functional theory analysis of the influence of pressure on ferrocene diffusion adds support for the idea that intercalation kinetics are altered by changing internal pressure. The results show solvent environments can be responsible for altering the effective pressure within intercalation hosts, influencing intercalation rates and product selection, even if the solvents do not react directly with the host solids.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723941","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":"Extrinsic and Intrinsic Factors Governing the Electrochemical Oxidation of Propylene in Aqueous Solutions","authors":"Tae Gyu Yun, Boqiang Chen, Sarah Wells, Younghwan Lim, Jun Seop Kim, Ana Guilherme Buzanich, Martin Radtke, Matthias M. Waegele, Marcel Risch, Alexis Grimaud","doi":"10.1021/jacs.5c02585","DOIUrl":"https://doi.org/10.1021/jacs.5c02585","url":null,"abstract":"The electrochemical synthesis of commodity chemicals such as epoxides and glycols offers a sustainable alternative to conventional methods that involve hazardous chemicals. Efforts to improve the yield and selectivity of propylene oxidation using Pd-based catalysts have been shown to be highly sensitive to applied potential, pH, and electrochemical cell design. Record efficiencies and yields were obtained by substitution of PdO by 4d or 5d transition metals, including Pt, with thus far little rationale regarding the origin for the improvement. Through electrochemical analysis, scanning transmission electron microscopy, X-ray absorption spectroscopy, and surface-enhanced infrared absorption spectroscopy, we investigated the mechanism of propylene oxidation on Pd-based catalysts. We demonstrate that adsorbates forming on PdO, where Pd adopts a square-planar coordination [PdO₄], differ from that forming on the surface of oxidized metallic Pd catalysts with an oxo intermediate mediating propylene oxidation on PdO. We further show that Pt substitution in PdO does not modify this oxo intermediate. Varying pH, we found that the onset for propylene oxidation is pH independent, indicating a potential-determining step where the proton is not involved in and similar reaction pathway in acidic and near-neutral conditions. Finally, our work undoubtedly demonstrates that high Faradaic efficiency toward propylene glycol and propylene oxide formation, such as those previously reported in the literature, can be achieved by means of electrode engineering and mastery of mass transport and local pH. Notably, we achieved ≈100% faradaic efficiency for propylene glycol at 1.7 V vs RHE in acidic media using a Pt-substituted PdO catalyst loaded onto a gas diffusion electrode.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"58 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734383","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":"A Systematic Approach for Incorporating Structural Flexibility in High-Throughput Computational Screening of Metal–Organic Frameworks for Xylene Separation","authors":"Saad Aldin Mohamed, Rui Zheng, Nengxiu Zhu, Dan Zhao, Jianwen Jiang","doi":"10.1021/jacs.5c01749","DOIUrl":"https://doi.org/10.1021/jacs.5c01749","url":null,"abstract":"Separation of xylene isomers poses a significant challenge due to their similar physicochemical properties. Currently, zeolites are utilized as adsorbents for this purpose in the chemical industry despite suboptimal separation performance. With tunable pore size and chemical functionality, metal–organic frameworks (MOFs) are promising adsorbents for separation. By virtue of high-throughput computational screening (HTCS), the adsorption performance of a large collection of MOFs can be evaluated <i>in silico</i> by using Monte Carlo (MC) simulations. Unlike prior studies assuming rigid structures of MOFs during screening, we develop a systematic approach for incorporating flexibility in HTCS for xylene separation. First, MOFs are judiciously classified with external flexibility (volume/shape changes) and internal flexibility (intraframework fluctuations), respectively, based on the nature and extent of structural deformation from molecular dynamics (MD) simulations. Afterward, adsorption in MOFs with external flexibility is simulated by hybrid MC/MD method, the flexible snapshot method is used for MOFs with a sort of internal flexibility, and grand-canonical MC (GCMC) method is employed for MOFs with negligible flexibility. Finally, top-performing MOFs are identified for xylene separation. While substantially reducing computational cost, this study also delivers more reliable results compared to the assumption of rigid structures. The HTCS approach is versatile and can be extended beyond MOFs, offering a robust tool for the virtual screening of other soft-porous materials for a wide range of important applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"215 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723851","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":"Rational Design Principles for De Novo α-Helical Peptide Barrels with Dynamic Conductive Channels","authors":"Ai Niitsu, Andrew R. Thomson, Alistair J. Scott, Jason T. Sengel, Jaewoon Jung, Kozhinjampara R. Mahendran, Mikiko Sodeoka, Hagan Bayley, Yuji Sugita, Derek N. Woolfson, Mark I. Wallace","doi":"10.1021/jacs.4c13933","DOIUrl":"https://doi.org/10.1021/jacs.4c13933","url":null,"abstract":"Despite advances in peptide and protein design, the rational design of membrane-spanning peptides that form conducting channels remains challenging due to our imperfect understanding of the sequence-to-structure relationships that drive membrane insertion, assembly, and conductance. Here, we describe the design and computational and experimental characterization of a series of coiled coil-based peptides that form transmembrane α-helical barrels with conductive channels. Through a combination of rational and computational design, we obtain barrels with 5 to 7 helices, as characterized in detergent micelles. In lipid bilayers, these peptide assemblies exhibit two conductance states with relative populations dependent on the applied potential: (i) low-conductance states that correlate with variations in the designed amino-acid sequences and modeled coiled-coil barrel geometries, indicating stable transmembrane α-helical barrels; and (ii) high-conductance states in which single channels change size in discrete steps. Notably, the high-conductance states are similar for all peptides in contrast to the low-conductance states. This indicates the formation of large, dynamic channels, as observed in natural barrel-stave peptide channels. These findings establish rational routes to design and tune functional membrane-spanning peptide channels with specific conductance and geometry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"183 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723940","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":"Enantioselective Dearomative [2π + 2σ] Photocycloaddition of Naphthalene Derivatives with Bicyclo[1.1.0]butanes Enabled by Gd(III) Catalysis","authors":"Wen-Jie Shen, Xin-Xuan Zou, Muzi Li, Yuan-Zheng Cheng, Shu-Li You","doi":"10.1021/jacs.5c01506","DOIUrl":"https://doi.org/10.1021/jacs.5c01506","url":null,"abstract":"The cycloaddition reactions of bicyclo[1.1.0]butanes with alkenes, imines, nitrones, or aziridines have served as an efficient platform to create conformationally restricted saturated bicyclic scaffolds. However, the use of readily available aromatics in such reactions, especially in an asymmetric manner, remains underexplored. Herein, we report a highly regio- and enantioselective dearomative [2π + 2σ] photocycloaddition reaction between naphthalene derivatives and bicyclo[1.1.0]butanes, enabled by Gd(III) catalysis. Bicyclo[1.1.0]butanes and naphthalenes adorned with a diverse array of functional groups are well-tolerated under mild conditions, affording enantioenriched pharmaceutically important bicyclo[2.1.1]hexanes in 30–96% yields with 81–93% ee and 12:1 → &gt;20:1 rr. The synthetic versatility of this reaction is further demonstrated by the facile removal of directing group and derivatizations of the dearomatized product. UV–vis absorption spectroscopy studies suggest the involvement of an excited naphthalene species in the reaction process.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"27 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723850","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}