Journal of the American Chemical Society最新文献

{"title":"An Experimental Benchmark for the Barrier Height of an On-Surface Reaction: Hydrogen Oxidation on Pt(332).","authors":"Florian Nitz,Stefan Hörandl,Michael Schwarzer,Theofanis Kitsopoulos,Daniel J Auerbach,Alec M Wodtke","doi":"10.1021/jacs.5c12862","DOIUrl":"https://doi.org/10.1021/jacs.5c12862","url":null,"abstract":"Developing predictive theories for the rates of reactions between surface-bound molecules is a central challenge to understanding many important phenomena including: heterogeneous catalysis, electrocatalysis, nanofabrication, and corrosion. To meet this challenge, chemically accurate benchmarks to test theoretically derived reaction rates and barrier heights are essential, but few exist. Here, we determine from experiment an accurate zero-point-energy corrected barrier height, 0.76 ± 0.03, for the reaction O* + H* → OH* occurring at atomic Pt B-type step sites, the rate limiting step of hydrogen oxidation on Pt. This experimental benchmark agrees with density functional theory (DFT) predictions made at the level of the generalized gradient approximation (GGA) for five different functionals, exhibiting a mean absolute error (MAE) of 25 meV. This is far better agreement than commonly expected for this level of theory. We speculate that this level of agreement may be a common feature for reactions that involve only species adsorbed on surfaces.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"21 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209340","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":"Heterogeneous Integration of Single-Crystalline Organic Semiconductor Microstructures via Capillary Condensation.","authors":"Fengmian Li,Junchuan Yang,Yuyan Zhao,Ke He,Xiao Wei,Jiangang Feng,Hanfei Gao,Jing Li,Ning Guo,Tianchen Li,Tenglong Li,Yifei Cheng,Zhenglian Qin,Yuchen Qiu,Zhiyuan He,Lei Jiang,Yuchen Wu","doi":"10.1021/jacs.5c12461","DOIUrl":"https://doi.org/10.1021/jacs.5c12461","url":null,"abstract":"Single-crystalline organic emissive semiconductors, featuring high photoluminescence quantum efficiency, intrinsic optical microcavities, and high charge carrier mobility, hold great promise for integrated photonics applications. However, realizing practical integrated photonics requires the deterministic patterning of multicomponent single-crystalline organic semiconductors with high resolution and unidirectional crystallographic orientation, which remains an ongoing challenge. Here, we report a nanoconfined recrystallization strategy that enables the integrated patterning of multicomponent, single-crystalline organic microstructures. By precisely regulating site-specific capillary condensation within top-pillar-confined spaces, we achieve selective rewetting of printed polycrystalline semiconductors, leading to the formation of discrete multicomponent nanoconfined liquid bridges without cross-contamination. Controlled nucleation and directional growth under regulated evaporation conditions yielded well-defined single-crystalline microstructures with a uniform size and pure crystallographic orientation. These multicomponent heterogeneous microstructures achieve a minimum feature size and interfeature spacing of 2 μm, representing a significant advancement over conventional patterning methods. These high crystalline structures demonstrate excellent optical microcavity characteristics, achieving an ultralow lasing threshold of 0.49 μJ cm-2 and quality factor (Q) as high as 1.1 × 104. Leveraging this platform, we fabricated 2 in. full-color organic single-crystalline microlaser arrays with pixel densities exceeding 2000 PPI (pixels per inch) and a color gamut coverage of 104% of the Rec. 2020.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"23 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209342","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":"Au-Mn Bond Formal Metathesis with Ar-F via Synergistic Bimetallic Activation.","authors":"Siyu Xia,Weina Zhong,Tingrui Li,Zhongren Xu,Jie Han,Wukun Liu,Weipeng Li,Chengjian Zhu,Jin Xie","doi":"10.1021/jacs.5c13893","DOIUrl":"https://doi.org/10.1021/jacs.5c13893","url":null,"abstract":"Selective C-F activation with gold-complex has been esteemed as a long-standing issue owing to a kinetically unfavorable oxidative addition elementary reaction. Herein, we report a synergistic bimetallic Au-Mn bond formal metathesis with aromatic C(sp2)-F bond, establishing a versatile platform for the synthesis of polyfluorophenyl-substituted Au(I) complexes. A wide range of structurally diverse L-Au(I)-ArFn complexes (37 examples, up to 98% yield) have been readily constructed. Mechanistic studies together with DFT calculations support that the key C-F bond cleavage proceeds via thermodynamically and kinetically feasible Au-Mn bimetallic cooperative activation, rather than direct oxidative addition toward either Au or Mn metal center. Notably, these aryl gold(I) complexes exhibit broad biological functions, including anticancer and/or anti-inflammatory efficacy, facilitating promising candidate drug discovery for pharmaceutical development. This bimetallic strategy should open new avenues to achieve unique reactivity profiles and novel mechanistic pathways.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"10 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209343","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":"An Amino-trans-Dihydrido Cobalt(III) Catalyst for Asymmetric Hydrogenation Reactions.","authors":"Zeming Wang,Minhao Li,Weiwei Zuo","doi":"10.1021/jacs.5c15142","DOIUrl":"https://doi.org/10.1021/jacs.5c15142","url":null,"abstract":"The development and fundamental chemistry of an amino-trans-dihydrido Co(III) catalyst for asymmetric hydrogenation (AH) reactions are described in this work. With an enantiopure tetradentate (S,S)-amino-ene(amido)diphosphine ligand defining the equatorial plane, axial trans-dihydrido coordination donors are incorporated into a cobalt(III) center with an octahedral coordination geometry. This cobalt complex serves as a novel amino-trans-dihydrido cobalt(III) catalyst (C1) for AH of ketones and esters. The introduction of these dihydrido ligands to C1 occurs in the precatalyst activation process, which involved substituting the bidentate acetylacetonato (acac) ligand in the amino-ene(amido)diphosphine Co(III) acac precatalyst (PC1) with trans-located dihydride ligands derived from dihydrogen gas. The molecular structure of C1 was characterized using 1H and 31P{1H} nuclear magnetic resonance (NMR) spectroscopy, and a comparative analysis of calculated 31P NMR chemical shifts versus the experimental values was conducted to further confirm the molecular structure of C1. C1 exhibited an unexpectedly high turnover frequency (TOF) of up to 9.9 s-1 and an enantiomeric excess (e.e.) of up to 99% in the AH of a wide range of ketone substrates under mild conditions. This efficiency, particularly for diaryl ketone substrates, was 66-90 times greater than those achieved with precious metal (ruthenium and iridium) catalysts and 8 503 times greater than those reported for cobalt catalysts chelated with other chiral ligands. The practical synthetic application of this cobalt catalyst was demonstrated through the synthesis of (R)-inabenfide, a plant growth regulator, with 95% e.e., at the 50 g scale. Kinetic studies determined that the H2 activation by a cobalt catalyst was the turnover-limiting step. For reactions conducted in toluene at 303 K, with [C1] = (0.36-1.52) × 10-4 M, [ketone] = (0.95-1.89) M, and H2 pressure = 50-70 bar, the rate law was rate = k[C1][H2], with k = (0.74-3.84) × 105 M-1 h-1, ΔH⧧ = 7.8 kcal mol-1, and ΔS⧧ = -35.9 cal mol-1 K-1. Density functional theory (DFT) calculations revealed that the enantio-determining step of the ketone reduction by C1 has a minimum energy barrier of 7.0 kcal mol-1. Analysis of the catalyst structure and performance revealed that the trans-located hydride ligand at C1 activates the catalyst for the hydrogenation of ketone substrates, while the NH functionality enables an outer-sphere H2 heterolytic splitting pathway that proceeds through a low-energy barrier. This active catalyst also catalyzed the hydrogenation of more challenging esters under mild conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"120 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209344","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":"The Interplay between Luminescence Dissymmetry Factor and Quantum Yield: Symmetric and Asymmetric Hydrogen Bonding.","authors":"Zhaoyu Wang,Xin Zeng,Wenkai Zhao,Yunchao Miao,Haolin Lu,Hebin Wang,Tianyin Shao,Xinyi Niu,Sehrish Gull,Tianjiao Qiao,Bing Sun,Xinfeng Liu,Hao-Li Zhang,Yongsheng Chen,Guankui Long","doi":"10.1021/jacs.5c13847","DOIUrl":"https://doi.org/10.1021/jacs.5c13847","url":null,"abstract":"Unraveling the luminescence-structure relationship in metal-free chiral perovskites remains challenging, particularly for achieving both a strong circularly polarized luminescence (CPL) and high photoluminescence quantum yield (PLQY). Here, we attempt to decode this hidden linkage by constructing the isomorphic polymorph-based metal-free chiral perovskite through the rational design of the A-site cation. The distinct steric hindrance between meta- and ortho-ammonium sites in 2-methylpiperazine-1,4-diium provides two possibilities for forming the hydrogen bond, which could control the crystallization pathways. Therefore, two different metal-free chiral perovskite polymorphs (A and B) with symmetric or asymmetric hydrogen bonding were obtained, which exhibit a remarkable difference in PLQY (36.51% vs 1.85%) and photoluminescence dissymmetry factor (|glum|, 0.032 vs 0.066). The highly luminescent polymorph A demonstrates stronger intermolecular coupling mediated by the symmetric hydrogen bonding, which effectively suppresses the nonradiative decay through rigidification of the octahedral framework, thereby enhancing the PLQY. In contrast, the asymmetric hydrogen bonding in polymorph B induces a greater structural distortion, which enhances the electron-phonon coupling and consequently reduces the PLQY. However, this asymmetric hydrogen bonding promotes efficient chirality transfer, leading to an increase of |glum|. Our work provides a molecular-level understanding of symmetric and asymmetric hydrogen bonding to determine the crystal packings and exciton dynamics, and thus the luminescence dissymmetry factor and quantum yield.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"98 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209347","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":"Efficient, Versatile, and Durable Electrocatalytic Nitroaromatic-to-Arylamine Reduction via Heteroatom-Site Hydrogen-Atom Transfer.","authors":"Pan Ran,Fenfei Wei,Beiyao Xiang,Aoqian Qiu,Bailin Tian,Xinrui Xu,Luhan Dai,Haowen Zhang,Fangyuan Wang,Yamei Sun,Yang Lv,Xixi Hu,Daiqian Xie,Mengning Ding","doi":"10.1021/jacs.5c11419","DOIUrl":"https://doi.org/10.1021/jacs.5c11419","url":null,"abstract":"The selective reduction of nitroaromatics to arylamines affords key intermediates for the industrial production of diverse chemical stocks and materials. The current reduction strategies generally work under harsh conditions, including high temperature, high pressure, and the use of hazardous hydrogen gas, leading to substantial challenges in sustainability and energy efficiency. To this end, direct electrocatalytic nitroaromatic reduction (with water-originated green hydrogen source) is a promising solution to these issues; however, their industrial applications are limited by the low selectivity, low current density, and poor stability of the catalytic electrodes. Here, we report a universally applicable, efficient, and selective electrocatalytic nitroaromatic-to-arylamine reduction approach utilizing highly stable self-standing Ru1Cu alloy electrodes. Superior performance (e.g., >99% selectivity, >99% yield, and >99% Faradaic efficiency for p-nitrophenol-to-p-aminophenol) can be achieved under mild working conditions and industrial-level current densities, which can be upheld over a wide range of working potentials (∼500 mV), pH values (0-14), and substrate concentrations (12.5-250 mM), and further extended to broad scope of nitroaromatics substrates and drugs. Moreover, we demonstrate the durable operation of electrolysis for over 1000 h in a flow reactor and kilogram-level production of p-aminophenol. Mechanistic investigations revealed that the superior catalytic performance originated from a switch from the PCET pathway to the HAT pathway as a result of the ensemble effect in Ru1Cu, enabling a heteroatom-site bimolecular microkinetic model with significantly promoted activation of surface hydrogen species (*H) and balanced surface bimolecular reaction kinetics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"75 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209047","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":"Post-Synthetic Modification-Induced Structural Transformations of 413 and 814 Metalla-Links via Sequential Oxidation of Dibenzothiophene Moieties.","authors":"Shu-Jin Bao,Yan Zou,Guo-Xin Jin","doi":"10.1021/jacs.5c11669","DOIUrl":"https://doi.org/10.1021/jacs.5c11669","url":null,"abstract":"Investigating stimulus-responsive structural transformations of complex mechanically interlocked molecules (MIMs) is key to better understanding the dynamic behaviors of biological macromolecules. Herein, we integrated oxidation-reactive dibenzothiophene moieties into organic frameworks, which self-assembled with binuclear half-sandwich organometallic clips of varying lengths, achieving selective construction of a linear [3]catenane (413 metalla-link) and an exceptionally rare closed four-link chain (CFLC, 814 metalla-link), the latter representing a synthetically challenging, highly interlocked topology. Topological transformation of the linear [3]catenane into a metalla-macrocycle was driven by substantial steric repulsion induced by bulky sulfone groups upon full oxidation with 3-chloroperoxybenzoic acid. By contrast, the CFLC exhibited remarkable topological stability against oxidative modifications, consistently preserving 814 link topology throughout the sequential oxidation process despite in situ structural transformations, yielding sulfoxide- and sulfone-containing CFLC derivatives. All nonoxidized and oxidized supramolecular assemblies were comprehensively characterized using single-crystal X-ray diffraction, high-resolution electrospray ionization mass spectrometry, and nuclear magnetic resonance spectroscopy. This work unveils a new pathway for postsynthetic modification of MIMs and provides critical insights into chemically driven transformations of complex, higher-order interlocked architectures, with significant potential to mimic nature's sophisticated, dynamic molecular systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"17 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209341","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":"Mechanistic Insights into the Borane-Mediated Conversion of 5-Carboxylcytosine to Dihydrouracil in DNA Enable an Efficient Labeling Method Using Alkoxyamines.","authors":"Cong Ding,Zipeng Wang,Bing-Wen Li,Jiangtian Shao,Ying Tang,Wei Yang,Xiaocheng Weng,Zhi-Xiang Yu,Xiang Zhou,Yibin Liu","doi":"10.1021/jacs.5c13154","DOIUrl":"https://doi.org/10.1021/jacs.5c13154","url":null,"abstract":"TET-assisted pyridine borane sequencing (TAPS) is a powerful method for mapping cytosine modifications, yet the underlying mechanism of conversion of 5-carboxylcytosine (5caC) to dihydrouracil (DHU) remains poorly understood. Here, through both experimental and computational studies, we show that the reaction proceeds via reduction and decarboxylation to give 5,6-dihydrocytidine as the intermediate, which is then slowly hydrolyzed to DHU as the rate-limiting step. We also found that in double-stranded DNA, the reaction can be catalyzed by an adjacent 5caC with high efficiency. The mechanistic discovery of the slow hydrolysis step by water in the conventional TAPS guided us to use more nucleophilic alkoxyamines to improve this protocol, achieving complete conversion within 1 h. This approach, when coupled with a click-chemistry pull-down, enables up to a 47-fold enrichment of 5caC-containing DNA. Our work thus provides fundamental mechanistic insights into a key epigenetic sequencing reaction and translates this knowledge into a new chemical biology tool for the selective labeling of DNA modifications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"98 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209345","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":"Alkenyl- and Aryl-Borane Nucleophiles in Enantioselective Iridium-Catalyzed Allylic Substitution of Vinyl Epoxides.","authors":"Jiangwei Wen,Lushuai Zhang,Chengyu He,Su-Min Song,Jasper L Tyler,Robert S Paton,Varinder K Aggarwal","doi":"10.1021/jacs.5c10680","DOIUrl":"https://doi.org/10.1021/jacs.5c10680","url":null,"abstract":"The catalytic asymmetric Petasis reaction represents a practical approach for synthesizing highly valuable chiral amine building blocks. However, despite the potential that this reactivity provides, the extension of the mechanistic framework to alternative electrophilic fragments is noticeably underdeveloped. We report herein the first Ir-catalyzed allylation of alkenyl, aryl, and alkynyl boranes with racemic vinyl epoxides or vinyl aziridines via an enantioselective 1,4-boronate rearrangement. Mechanistic studies reveal that the high levels of stereoselectivity arise due to tandem dynamic kinetic resolution and kinetic resolution processes, with computational analysis suggesting that a stabilizing interaction between the alkenyl boronate π-system and the electrophile facilitates the key transition state. The utility of this methodology is demonstrated in a concise, enantioselective two-step synthesis of the phytotoxin (R)-pyricuol.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"10 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203686","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":"Rapid Activation of Amino Acids with Cyanide and Hypochlorite.","authors":"Luke K Marshall,Ruiqin Yi,Joshua J Brown,Albert C Fahrenbach","doi":"10.1021/jacs.5c12639","DOIUrl":"https://doi.org/10.1021/jacs.5c12639","url":null,"abstract":"Cyanogen chloride (NCCl) produced from the reaction of -CN with HOCl has previously been shown to afford activation of ribonucleotides. We now report that NCCl reacts with primary aliphatic amino acids to rapidly produce N-carbamoyl dipeptides in excellent yields (89-98%). Studies with l-alanine suggest that racemization of the amino acids does not occur significantly during the reaction. Quantum chemical (DFT) calculations predict that the mechanism proceeds via activated 2-amino-5(4H)-oxazolone intermediates, which undergo amino acid nucleophilic attack. NCCl can also be generated in situ from glycine and HOCl, enabling the \"sacrificial activation\" of glycine to form N-carbamoyl diglycine. At 70 °C, selective peptide bond hydrolysis yields N-carbamoyl glycine, which is a known peptide precursor. The findings herein build upon prior work involving NCCl in prebiotic ribonucleotide synthesis and activation, highlighting its potential as a general chemical activator for the prebiotic condensation of life's molecular building blocks.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"114 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203724","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}