Journal of the American Chemical Society最新文献_第2页

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c16328

Jacklin H. Smith, Daniel Čavlović, Luke T. Lackovic, Miguel Medina Lopez, Elena Meirzadeh, Michael L. Steigerwald, Xavier Roy, Colin P. Nuckolls, Scott R. Docherty

引用次数: 0

Merging and Clipping Nets for the Synthesis of Three- and Two-Merged Net Metal–Organic Frameworks

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c15936

Yunhui Yang, Pilar Fernández-Seriñán, Borja Ortín-Rubio, Partha Samanta, Felipe Gándara, Davide M. Proserpio, Dongsik Nam, Judith Juanhuix, Inhar Imaz, Daniel Maspoch

{"title":"Merging and Clipping Nets for the Synthesis of Three- and Two-Merged Net Metal–Organic Frameworks","authors":"Yunhui Yang, Pilar Fernández-Seriñán, Borja Ortín-Rubio, Partha Samanta, Felipe Gándara, Davide M. Proserpio, Dongsik Nam, Judith Juanhuix, Inhar Imaz, Daniel Maspoch","doi":"10.1021/jacs.4c15936","DOIUrl":"https://doi.org/10.1021/jacs.4c15936","url":null,"abstract":"Herein, we report how merging and clipping nets in metal–organic frameworks (MOFs) can be controlled in a single-crystal-to-single-crystal fashion using three different approaches─the merged net, clip-off chemistry, and linker reinstallation─to design and synthesize three- and two-merged net MOFs. Initially, we show the formation of three isoreticular three-merged net MOFs by linking a trimeric Sc3+ cluster, Sc3(μ3-Ο)(−COO)6, with ditopic zigzag and tritopic linkers. The resulting MOFs exhibit three-merged edge-transitive nets─kgd + hxl + pcu─for the first time. Then, using these three-merged net MOFs as precursors, we selectively remove one of these subnets, the hxl net, via clip-off chemistry to form two-merged net MOFs. This process involves the cleavage of olefinic groups via ozonolysis, providing the resulting two-merged net MOFs with free carboxylic acid groups that can be used to tune their sorption properties such as the removal of cationic organic pollutants. Finally, we use the linker reinstallation approach to convert the two-merged net MOFs back to the three-merged net MOFs. This approach allows for the postsynthetic addition of the previously removed hxl merged net, enabling recovery of the initial three-merged net MOFs or synthesis of new ones using novel ditopic zigzag linkers.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880133","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}

引用次数: 0

Reversible Bimetallic Inhibition to Modulate Selectivity During Catalysis

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c15359

Emmanuel Serrano-Díez, Alejandra Pita-Milleiro, Jesús Rangel-García, Juan J. Moreno, Marta Roselló-Merino, Jesús Campos

{"title":"Reversible Bimetallic Inhibition to Modulate Selectivity During Catalysis","authors":"Emmanuel Serrano-Díez, Alejandra Pita-Milleiro, Jesús Rangel-García, Juan J. Moreno, Marta Roselló-Merino, Jesús Campos","doi":"10.1021/jacs.4c15359","DOIUrl":"https://doi.org/10.1021/jacs.4c15359","url":null,"abstract":"Bimetallic complexes have demonstrated a great ability to enhance the activity of monometallic systems for bond activation and catalysis. In this work, we explore the opposite approach: using a second metal to passivate the activity of another by reversible bimetallic inhibition. To do so we have synthesized a family of nine electrophilic gold complexes of formula Au(PR3)(NTf2) ([NTf2]− = [N(SO2CF3)2]−) that can act as inhibitors in the semihydrogenation of terminal and internal alkynes catalyzed by the iconic iridium Vaska complex IrCl(CO)(PPh3)2. This behavior parallels the well-known passivation effect of lead over palladium in the heterogeneous Lindlard catalyst. Most gold fragments, except for the most hindered, form metal-only Lewis pairs upon combination with iridium, which have been fully characterized and exhibit distinct dative Ir → Au bonds. When applied to alkyne hydrogenation, these bimetallic structures have a clear tendency toward olefin formation, while the monometallic catalyst unselectively leads to overreduction products. Our computational studies not only provide a feasible mechanism for the Ir-only system, but also evince the active role of gold in passivating iridium by reversibly forming heterobimetallic structures that lead to enhanced selectivity.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874256","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}

引用次数: 0

High Molecular Weight Uniform Polymers Encoding Octal Sequences by Passerini Iterative Exponential Growth

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c13528

Valene Wang, Su Bin Park, Soo Jeong Lee, Mo Beom Koo, Kyoung Taek Kim

{"title":"High Molecular Weight Uniform Polymers Encoding Octal Sequences by Passerini Iterative Exponential Growth","authors":"Valene Wang, Su Bin Park, Soo Jeong Lee, Mo Beom Koo, Kyoung Taek Kim","doi":"10.1021/jacs.4c13528","DOIUrl":"https://doi.org/10.1021/jacs.4c13528","url":null,"abstract":"Sequence-defined polymers composed of a large pool of chemically distinct monomers (SDPs) have been pursued to achieve the structural and functional precisions exhibited by biopolymers in nonbiological environments. In contrast to the incremental growth of SDPs by sequential addition of individual monomers, the iterative exponential growth (IEG) method allows the synthesis of high molecular-weight SDPs, but their sequences have been composed mostly of binary monomers. Consequently, achieving high molecular-weight SDPs built with a large pool of monomers remains a challenge. Here we report the Passerini iterative exponential growth (P-IEG) approach that enables efficient synthesis of 128-mer uniform poly(hydroxybutyrate) (PHB), possessing 127 γ-acylamino cyclohexyl side groups (27 kDa, Đ = 1) and a 31-mer SDP, encoding an octal sequence composed of eight chemically distinct repeating units. Taking advantage of the combinatorial character of the Passerini three-component reaction involving an aldehyde, a carboxylic acid, and an isocyanide to form an acyloxy amide linkage, we simultaneously achieved the exponential chain growth through the convergence of bifunctional building blocks and side-chain implementation by selecting appropriate isocyanides as a third component. The P-IEG approach enabled the synthetic encoding of complex information, an octal sequence equivalent to a 93-bit binary code, into a 31-mer SDP. Our proposed P-IEG method could contribute to the synthesis of synthetic macromolecules with absolutely defined sequences of functionalities. These polymers could be used for the development of functional materials with properties not achievable by conventional polymers, including polymers storing digital information at higher density.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 4 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874378","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}

引用次数: 0

The Role of Nonequilibrium Solvent Effects in Enhancing Direct CO2 Capture at the Air–Aqueous Amino Acid Interface

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c14612

Nitesh Kumar, Vyacheslav S. Bryantsev, Santanu Roy

{"title":"The Role of Nonequilibrium Solvent Effects in Enhancing Direct CO2 Capture at the Air–Aqueous Amino Acid Interface","authors":"Nitesh Kumar, Vyacheslav S. Bryantsev, Santanu Roy","doi":"10.1021/jacs.4c14612","DOIUrl":"https://doi.org/10.1021/jacs.4c14612","url":null,"abstract":"Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO2 from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling ab initio molecular dynamics simulations. We elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH2], facilitating SN2-based CO2 conversion to a zwitterion, which then releases a proton via overhydration of [-NH2]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO2 capture kinetics via control of solvation and ion paring.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874380","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}

引用次数: 0

Molecular Hydride Superconductor BiH4 with Tc up to 91 K at 170 GPa

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c15137

Pengfei Shan, Liang Ma, Xin Yang, Mei Li, Ziyi Liu, Jun Hou, Sheng Jiang, LiLi Zhang, Lifen Shi, Pengtao Yang, Chuanlong Lin, Bosen Wang, Jianping Sun, Haizhong Guo, Yang Ding, Huiyang Gou, Zhongxian Zhao, Jinguang Cheng

{"title":"Molecular Hydride Superconductor BiH4 with Tc up to 91 K at 170 GPa","authors":"Pengfei Shan, Liang Ma, Xin Yang, Mei Li, Ziyi Liu, Jun Hou, Sheng Jiang, LiLi Zhang, Lifen Shi, Pengtao Yang, Chuanlong Lin, Bosen Wang, Jianping Sun, Haizhong Guo, Yang Ding, Huiyang Gou, Zhongxian Zhao, Jinguang Cheng","doi":"10.1021/jacs.4c15137","DOIUrl":"https://doi.org/10.1021/jacs.4c15137","url":null,"abstract":"In pursuit of high-Tc hydride superconductors, the molecular hydrides have attracted less attention because the hydrogen quasimolecules are usually inactive for superconductivity. Here, we report on the successful synthesis of a novel bismuth hydride superconductor C2/c-BiH4 at pressures around 170–180 GPa. Its structure comprises bismuth atoms and elongated hydrogen molecules with a H–H bond length of 0.81 Å at 170 GPa, characterizing it as a typical molecular hydride. Transport measurements revealed the occurrence of superconductivity with Tc up to 91 K at 170 GPa, as evidenced by a sharp drop of resistivity to zero and a characteristic downward shift of Tc under magnetic fields. Calculations by density functional theory elucidate that both midfrequency H-derived phonons and low-frequency vibrations from Bi atoms are important for the strong electron–phonon coupling in BiH4, differentiating it from most high-Tc superconducting hydrides. Our work not only places C2/c-BiH4 among the molecular hydride superconductors with the highest Tc but also offers new directions for designing and synthesizing more high-Tc hydride superconductors.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"61 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874248","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}

引用次数: 0

Fluoroform (CHF3) Production from CF3CHO Photolysis and Implications for the Decomposition of Hydrofluoroolefins and Hydrochlorofluoroolefins in the Atmosphere

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c11776

Joshua D. Thomson, Jyoti S. Campbell, Ethan B. Edwards, Christopher Medcraft, Klaas Nauta, Maria Paula Pérez-Peña, Jenny A. Fisher, David L. Osborn, Scott H. Kable, Christopher S. Hansen

{"title":"Fluoroform (CHF3) Production from CF3CHO Photolysis and Implications for the Decomposition of Hydrofluoroolefins and Hydrochlorofluoroolefins in the Atmosphere","authors":"Joshua D. Thomson, Jyoti S. Campbell, Ethan B. Edwards, Christopher Medcraft, Klaas Nauta, Maria Paula Pérez-Peña, Jenny A. Fisher, David L. Osborn, Scott H. Kable, Christopher S. Hansen","doi":"10.1021/jacs.4c11776","DOIUrl":"https://doi.org/10.1021/jacs.4c11776","url":null,"abstract":"Hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are the leading synthetic replacements for compounds successively banned by the Montreal Protocol and amendments. HFOs and HCFOs readily decompose in the atmosphere to form fluorinated carbonyls, including CF3CHO in yields of up to 100%, which are then photolyzed. A long-standing issue, critical for the transition to safe industrial gases, is whether atmospheric decomposition of CF3CHO yields any quantity of CHF3 (HFC-23), which is one of the most environmentally hazardous greenhouse gases. This comprehensive experimental investigation employs purpose-built photoionization mass spectrometry, Fourier-transform infrared, and microwave spectroscopy techniques and confirms production of CHF3 following excitation at a tropospherically relevant wavelength (λ = 308 nm) and under atmospheric pressure conditions. Pressure-dependent CHF3 quantum (Φ) and molar (Y) yields are reported from Φ = Y = 0.16 ± 0.03 under collision-free conditions to Φ = (2.3 ± 0.3) × 10–4, Y = (1.17 ± 0.27) × 10–3 at 1 bar N2.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"53 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874376","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}

引用次数: 0

Conjugation Length Dependence of Intramolecular Singlet Fission in a Series of Regioregular Oligo 3-Alkyl(thienylene-vinylene)s

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c12877

Daniel W. Polak, Iain Andrews, Enrico Salvadori, Andrew J. Musser, Alexander Auty, Dimitri Chekulaev, Julia A. Weinstein, Martin Heeney, Jenny Clark

引用次数: 0

Heteroaryl-Directed Iridium-Catalyzed Enantioselective C–H Alkenylations of Secondary Alcohols

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-23 DOI: 10.1021/jacs.4c16414

Wenbin Mao, Craig M. Robertson, John F. Bower

引用次数: 0

Intercellular Ion-Gradient Piezoheterogated Biphasic Gel for Ultrahigh Iontronic Generation

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-22 DOI: 10.1021/jacs.4c13305

Weipeng Chen, Suli Zhang, Ao Zhang, Huirong Liu, Zhixin Wu, Linxin Zhai, Xiaomin Dong, Zhiping Xu, Ziguang Zhao, Liping Wen

{"title":"Intercellular Ion-Gradient Piezoheterogated Biphasic Gel for Ultrahigh Iontronic Generation","authors":"Weipeng Chen, Suli Zhang, Ao Zhang, Huirong Liu, Zhixin Wu, Linxin Zhai, Xiaomin Dong, Zhiping Xu, Ziguang Zhao, Liping Wen","doi":"10.1021/jacs.4c13305","DOIUrl":"https://doi.org/10.1021/jacs.4c13305","url":null,"abstract":"Piezoionic materials have attracted considerable attention for their ability to generate iontronic signals or power in response to stress stimuli. However, the limited intrinsic transport distinction between cations and anions within most ionic materials results in weakened iontronic power conversion efficiencies under stress fields. Here, we report a piezoheterogated biphasic gel for ultrahigh iontronic generation, characterized by high-internal microphase heterointerfaces that facilitate the distinct transport of various ion species. Due to the ion confinement effect of cell-like multicompartments, a stable intercellular ion gradient within biphasic gel systems can be established in situ, constructing the chemical potential to further enhance ionic transmission efficiency and obtain a high-density net ion flux in the piezoionic process. Consequently, as a reliable piezo cell, a record maximum power of 150 W/m3 over 24 h can be realized. Meanwhile, we develop piezoionic devices that can interface with paralyzed vagus nerves and successfully regulate the blood pressure of rodents through their neuromodulation. By matching the ion species with heterointerface gating effects to regulate the ionic transmission efficiency, the piezo signal neuromodulation process can be further governed. We anticipate that the bioinspired heterointerface engineering strategy can provide new insights into designing high-performance piezoionic systems for promising abiotic–biotic applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"22 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874404","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}

引用次数: 0