{"title":"Rational Control of Ionic Conduction of Encapsulated Ionic Liquid by Fluorination of Isoreticular Metal–Organic Frameworks","authors":"Tuo Di, Yukihiro Yoshida, Hiroshi Kitagawa","doi":"10.1021/jacs.5c02879","DOIUrl":"https://doi.org/10.1021/jacs.5c02879","url":null,"abstract":"Hybrid materials have attracted much attention in solid-state conductors because of their great advantage in various combinations of components. In this study, the control of ionic conductivity of ionic liquid (IL), which is encapsulated in micropores of metal–organic frameworks (MOFs), has been realized by the chemical modification of the ligands of MOFs for the first time. When IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ((EMI)(TFSA)), is encapsulated into the pores with a 50% volumetric filling level, it shows the highest ionic conductivity when encapsulated in the fluorous MOF among the three isoreticular zinc-based microporous MOFs; the ionic diffusivity is 1 order of magnitude higher than that of (EMI)(TFSA)-encapsulated non-fluorous MOF. Computational simulations indicate that the mobility of (EMI)(TFSA) in a non-fluorous framework is significantly restricted due to abundant C–H···F interactions, whereas the introduction of fluorine atoms on the ligands suppresses the C–H···F interactions, thereby showing the highest ionic conductivity. On the other hand, the ion migration of encapsulated (EMI)(TFSA) is not greatly affected by the fluorination of the ligands at a 100% filling level, because the possible different IL distributions with a 50% filling level are largely eliminated for the fully occupied (EMI)(TFSA).","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"75 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814094","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}
Spencer T. Burton, Gyunhee Lee, Curtis E. Moore, Christo S. Sevov, Claudia Turro
{"title":"Cyclometallated Co(III) Complexes with Lowest-Energy Charge Transfer Excited States Accessible with Visible Light","authors":"Spencer T. Burton, Gyunhee Lee, Curtis E. Moore, Christo S. Sevov, Claudia Turro","doi":"10.1021/jacs.4c18299","DOIUrl":"https://doi.org/10.1021/jacs.4c18299","url":null,"abstract":"The Co(III) complexes, <i>cis</i>-[Co(ppy)<sub>2</sub>(L)]PF<sub>6</sub>, where ppy = 2-phenylpyridine and L = bpy (2,2′-bipyridine; <b>1</b>), phen (1,10-phenanthroline; <b>2</b>), and DAP (1,12-diazaperylene; <b>3</b>), are reported and their photophysical properties were investigated to evaluate their potential as sensitizers for applications that include solar energy conversion schemes and photoredox catalysis. Calculations show that cyclometallation in the <i>cis</i>-[Co(ppy)<sub>2</sub>(L)]PF<sub>6</sub> series affords strong Co(dπ)/ppy(π) orbital interactions that result in a Co/ppy(π*) highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) localized on the diimine ligand, L(π*). Complexes <b>1–3</b> exhibit relatively invariant oxidation potentials, whereas the reduction event is dependent on the identity of the diimine ligand, L, consistent with the theoretical predictions. For <b>3</b> a broad Co/ppy(π*) → L(π*) metal/ligand-to-ligand charge transfer (ML-LCT) absorption band is observed in CH<sub>3</sub>CN with a maxima at 507 nm, extending beyond 600 nm. Upon excitation of the <sup>1</sup>ML-LCT transition, transient absorption features consistent with the population of a <sup>3</sup>ML-LCT excited state with lifetimes, τ, of 3.0 ps, 4.6 and 42 ps for <b>1</b>, <b>2</b> and <b>3</b> in CH<sub>3</sub>CN respectively are observed. Upon irradiation with 505 nm, <b>3</b> is able to reduce methyl viologen (MV<sup>2+</sup>), an electron acceptor commonly in photocatalytic schemes. To our knowledge, <b>3</b> represents the first heteroleptic molecular Co(III) complex that combines cyclometallation with a diimine ligand with lowest-lying metal-to-ligand charge transfer excited states able to undergo photoinduced charge transfer with low-energy green light. As such, the structural design of <b>3</b> represents an important step toward d<sup>6</sup> photosensitizers based on earth abundant metals.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"37 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814032","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}
Andrew J. Clough, Nicholas M. Orchanian, Jonathan M. Skelton, Abbey J. Neer, Sebastian A. Howard, Courtney A. Downes, Louis F. J. Piper, Aron Walsh, Brent C. Melot, Smaranda C. Marinescu
{"title":"Retraction of “Room Temperature Metallic Conductivity in a Metal–Organic Framework Induced by Oxidation”","authors":"Andrew J. Clough, Nicholas M. Orchanian, Jonathan M. Skelton, Abbey J. Neer, Sebastian A. Howard, Courtney A. Downes, Louis F. J. Piper, Aron Walsh, Brent C. Melot, Smaranda C. Marinescu","doi":"10.1021/jacs.5c00681","DOIUrl":"https://doi.org/10.1021/jacs.5c00681","url":null,"abstract":"The authors retract this Article (DOI: 10.1021/jacs.9b06898) because reinvestigation of the conductivity data for the cobalt 2,3,6,7,10,11-triphenylenehexathiolate (<b>CoTHT</b>) metal–organic framework (MOF) determined that the anomalous temperature-dependent maxima reported were not due to metallic conductivity. Instead, it was found that ohmic contact was lost during cooling. This resulted in a significant reduction to the current passing between the electrodes, which could not be detected using the equipment available at the time. The conductivity data for the iron analogue <b>FeTHT</b> was not remeasured, but the authors consider that the anomalous temperature-dependent maxima is due to a similar effect. The authors note that the density functional theory (DFT) calculations, synthetic studies, synchrotron X-ray powder diffraction, modeling, Brunauer–Emmett–Teller (BET) measurements, scanning electron microscopy and atomic force microscopy, photoemission, and magnetic susceptibility measurements stand on their own merit. However, due to the misinterpretation of the conductivity data, the findings of the work are incorrect, and thus the paper is being retracted. The original Article was published on September 25, 2019 and retracted on April 10, 2025. This article has not yet been cited by other publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814353","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}
Homare Arima, Shotaro Hiraide, Hiroyuki Nagano, Leila Abylgazina, Irena Senkovska, Günter K. Auernhammer, Andreas Fery, Stefan Kaskel, Satoshi Watanabe
{"title":"Atomic Force Microscopy Strategies for Capturing Guest-Induced Structural Transitions in Single Flexible Metal–Organic Framework Particles","authors":"Homare Arima, Shotaro Hiraide, Hiroyuki Nagano, Leila Abylgazina, Irena Senkovska, Günter K. Auernhammer, Andreas Fery, Stefan Kaskel, Satoshi Watanabe","doi":"10.1021/jacs.5c01377","DOIUrl":"https://doi.org/10.1021/jacs.5c01377","url":null,"abstract":"Flexible metal–organic frameworks (MOFs) exhibit stepped adsorption isotherms due to structural transitions between narrow-pore (np) and large-pore (lp) states. This characteristic stepwise uptake at a certain pressure results in adsorptive high working capacities, making these materials highly effective for energy-efficient gas storage and separation processes. The transition pressure, which is key to enhancing separation efficiency, can be tuned by varying the particle size of flexible MOFs. However, a comprehensive understanding of size-dependent effects has been limited due to particle size distribution in samples. Conventional adsorption measurements provide only averaged isotherms for powder samples, and analyzing the size effect at the single-particle level requires experimental techniques that can capture transition behavior of individual particles separately. This study utilized atomic force microscopy coupled with thermodynamic analysis to investigate guest-induced structural transitions. Force application to a MOF particle triggered a structural change from the lp to np state, generating force profiles that were analyzed to uncover the underlying transition mechanisms and calculate transition pressures using free energy analysis. The evaluation revealed distinct transition mechanisms for two flexible MOFs: ELM-12 exhibited a step-by-step mechanism, while DUT-8(Ni) displayed an all-at-once transition. Force profile analysis enabled precise determination of the free energy changes and transition pressures for individual particles. This approach provided detailed insights into the transition mechanisms and their impact on overall adsorption isotherms, offering a novel perspective on how single-particle behavior influences bulk material performance.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814091","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}
Maria Zacharopoulou, Neeleema Seetaloo, James Ross, Amberley D. Stephens, Giuliana Fusco, Thomas M. McCoy, Wenyue Dai, Ioanna Mela, Ana Fernandez-Villegas, Anne Martel, Alexander F. Routh, Alfonso De Simone, Jonathan J. Phillips, Gabriele S. Kaminski Schierle
{"title":"Local Ionic Conditions Modulate the Aggregation Propensity and Influence the Structural Polymorphism of α-Synuclein","authors":"Maria Zacharopoulou, Neeleema Seetaloo, James Ross, Amberley D. Stephens, Giuliana Fusco, Thomas M. McCoy, Wenyue Dai, Ioanna Mela, Ana Fernandez-Villegas, Anne Martel, Alexander F. Routh, Alfonso De Simone, Jonathan J. Phillips, Gabriele S. Kaminski Schierle","doi":"10.1021/jacs.4c13473","DOIUrl":"https://doi.org/10.1021/jacs.4c13473","url":null,"abstract":"Parkinson’s disease (PD) is linked to the aggregation of the intrinsically disordered protein α-synuclein (aSyn), but the precise triggers and mechanisms driving this process remain unclear. Local environmental factors, such as ion concentrations, can influence aSyn’s conformational ensemble and its tendency to aggregate. In this study, we explore how physiologically relevant ions, mainly Ca<sup>2+</sup> and Na<sup>+</sup>, affect aSyn aggregation, monomer structural dynamics, and fibril polymorphism. ThT fluorescence assays show that all ions speed up aggregation, with Ca<sup>2+</sup> having the strongest effect. Using heteronuclear single quantum correlation nuclear magnetic resonance (<sup>1</sup>H–<sup>15</sup>N HSQC NMR) spectroscopy, we validate that Ca<sup>2+</sup> binds at the C-terminus while Na<sup>+</sup> interacts nonspecifically across the sequence. Small-angle neutron scattering (SANS) and hydrogen–deuterium exchange mass spectrometry (HDX-MS) show that Na<sup>+</sup> leads to more extended aSyn structures, while Ca<sup>2+</sup> results in moderate extension. Molecular dynamics (MD) simulations support this, showing Na<sup>+</sup> increases extension between the NAC region and C-terminus, whereas Ca<sup>2+</sup> biases the ensemble toward a moderately elongated structure. MD also shows that Ca<sup>2+</sup> increases water persistence times in the hydration shell, indicating that aSyn aggregation propensity is due to a combination of conformational bias of the monomer and solvent mobility. Atomic force microscopy (AFM) points toward the formation of distinct fibril polymorphs under different ionic conditions, suggesting ion-induced monomer changes contribute to the diversity of fibril structures. These findings underscore the pivotal influence of the local ionic milieu in shaping the structure and aggregation propensity of aSyn, offering insights into the molecular underpinnings of PD and potential therapeutic strategies targeting aSyn dynamics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814030","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}
Paul Katzberger, Lea M. Hauswirth, Antonia S. Kuhn, Gregory A. Landrum, Sereina Riniker
{"title":"Rapid Access to Small Molecule Conformational Ensembles in Organic Solvents Enabled by Graph Neural Network-Based Implicit Solvent Model","authors":"Paul Katzberger, Lea M. Hauswirth, Antonia S. Kuhn, Gregory A. Landrum, Sereina Riniker","doi":"10.1021/jacs.4c17622","DOIUrl":"https://doi.org/10.1021/jacs.4c17622","url":null,"abstract":"Understanding and manipulating the conformational behavior of a molecule in different solvent environments is of great interest in the fields of drug discovery and organic synthesis. Molecular dynamics (MD) simulations with solvent molecules explicitly present are the gold standard to compute such conformational ensembles (within the accuracy of the underlying force field), complementing experimental findings and supporting their interpretation. However, conventional methods often face challenges related to computational cost (explicit solvent) or accuracy (implicit solvent). Here, we showcase how our graph neural network (GNN)-based implicit solvent (GNNIS) approach can be used to rapidly compute small molecule conformational ensembles in 39 common organic solvents reproducing explicit-solvent simulations with high accuracy. We validate this approach using nuclear magnetic resonance (NMR) measurements, thus identifying the conformers contributing most to the experimental observable. The method allows the time required to accurately predict conformational ensembles to be reduced from days to minutes while achieving results within one <i>k</i><sub>B</sub><i>T</i> of the experimental values.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"183 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814031","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}
Subhajit Pal, Erika E. Salzman, Dominic Ramirez, Hannah Chen, Cynthia A. Perez, Katelyn Dale, Sujoy K. Ghosh, Liwei Lin, Phillip B. Messersmith
{"title":"Versatile Solid-State Medical Superglue Precursors of α-Lipoic Acid","authors":"Subhajit Pal, Erika E. Salzman, Dominic Ramirez, Hannah Chen, Cynthia A. Perez, Katelyn Dale, Sujoy K. Ghosh, Liwei Lin, Phillip B. Messersmith","doi":"10.1021/jacs.4c18448","DOIUrl":"https://doi.org/10.1021/jacs.4c18448","url":null,"abstract":"α-Lipoic acid (<b>αLA</b>) is an attractive building block for medical adhesives. However, due to poor water solubility of <b>αLA</b> and high hydrophobicity of poly(αLA), elevated temperatures, organic solvents, or complex preparations are typically required to obtain and deliver <b>αLA</b>-based adhesives to biological tissue. Here, we report <b>αLA</b>-based powder and low-viscosity liquid superglues that polymerize and bond rapidly upon contact with wet tissue. A monomeric mixture of <b>αLA,</b> sodium lipoate, and an activated ester of lipoic acid was used to formulate the versatile adhesives. Stress–strain measurements of the wet adhesives confirmed the high flexibility of the adhesive. Moreover, a small molecule regenerative drug was successfully incorporated into and released from the adhesive without altering the physical and adhesive properties. In vitro and in vivo studies of the developed adhesives confirmed their cell and tissue compatibility, biodegradability, and potential for sustained drug delivery. Moreover, due to the inherent ionic nature of the adhesives, they demonstrated high electric conductivity and sensitivity to deformation, allowing for the development of a tissue-adherent strain sensor.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814033","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}
Kun Wu, Wei Zhao, Ling Huang, Wen-Ting Zeng, Qiang Zhu, Hao-Bo Wang, Qin-Hong Wang, Xiansong Shi, He Li, Weigang Lu, Guo-Hong Ning, Dan Zhao, Dan Li
{"title":"Aqueous-Phase Synthesis of Cyclic Trinuclear Cluster-Based Metal–Organic Frameworks","authors":"Kun Wu, Wei Zhao, Ling Huang, Wen-Ting Zeng, Qiang Zhu, Hao-Bo Wang, Qin-Hong Wang, Xiansong Shi, He Li, Weigang Lu, Guo-Hong Ning, Dan Zhao, Dan Li","doi":"10.1021/jacs.5c01434","DOIUrl":"https://doi.org/10.1021/jacs.5c01434","url":null,"abstract":"The synthesis of metal–organic frameworks (MOFs) often involves high-boiling-point organic solvents, which can have extensive environmental impact and limit their large-scale applications. Here, we present a one-pot aqueous-phase approach for the rapid preparation of 33 trinuclear-copper-cluster-based MOFs (<b>1</b> to <b>33</b>) with different pyrazoles under ultrasonic irradiation. To address the water-solubility challenge of organic linkers, we employ aromatic amines/aldehydes and pyrazole aldehydes/amines to <i>in situ</i> generate imine-based pyrazoles. This linker dismantling strategy enables the formation of low-concentration pyrazoles, which are essential for the assembly of trinuclear-copper-cluster-based MOFs in the aqueous phase. The use of preassembled trinuclear gold complexes instead of aromatic amines affords an Au–Cu-based MOF (<b>34</b>) of alternating gold and copper clusters, a rare example of MOFs with mixed yet precise arrangement of metal compositions. Additionally, the direct addition of pyruvic acid to the reaction mixture results in the facile synthesis of a carboxylic-acid-functionalized MOF (<b>35</b>), eliminating the need for preinstallation or postmodification steps in traditional MOF synthesis. Furthermore, we demonstrate <b>11-AA</b> as an efficient photocatalyst for cross-dehydrogenative coupling (CDC) reactions, exploiting the synergetic effect of substrate activation on the copper sites and subsequent coupling initiated by the photosensitive organic linkers. This work offers a simple solution for making MOFs with minimal environmental impact; it also opens up possibilities for developing multifunctional MOFs for diverse applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"108 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814092","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}
Zhuo-Qin Wang, Meng-Hao Li, Shuang Liang, Yuxiang Kong, Chunyu Wang, Lu Li, Ji-Jing Xu, Ying-Wei Yang
{"title":"Regulating Enol-to-Keto Tautomerization of Pillararene-Based Conjugated Macrocycle Polymers for H2O2 Photosynthesis","authors":"Zhuo-Qin Wang, Meng-Hao Li, Shuang Liang, Yuxiang Kong, Chunyu Wang, Lu Li, Ji-Jing Xu, Ying-Wei Yang","doi":"10.1021/jacs.5c00768","DOIUrl":"https://doi.org/10.1021/jacs.5c00768","url":null,"abstract":"Porous organic polymers have emerged as promising materials for energy conversion, pollutant adsorption, and heterogeneous catalysis because of their tunable pore structures and high surface areas. However, most porous organic polymers are still limited by insufficient conjugation and inefficient electron–hole separation, hindering the tunability of their photoelectric properties and overall functionality. By integrating macrocyclic compounds as a new building block, which feature electron-rich cavities and rigid ring structures, into the polymer network, the resulting conjugated macrocycle polymers are expected to provide an innovative approach to enrich the photoelectric functionalities of porous organic polymers. Herein, an enaminone-based pillararene photocatalyst, TpAP[5], is constructed by covalently linking functionalized pillar[5]arene to conjugated macrocycle polymers through Schiff base condensation for efficient photocatalytic reactions. This material demonstrates exceptional performance in the photocatalytic production of hydrogen peroxide, achieving a rate of 2343 μmol g<sup>–1</sup> h<sup>–1</sup>. In-depth investigations reveal that the incorporation of pillararenes enables synergistic catalysis of water oxidation and oxygen reduction reactions and significantly enhances catalyst stability by regulating molecular tautomerization. This work opens new avenues for designing high-performance multifunctional conjugated macrocycle polymers with significant potential for clean energy conversion.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"246 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814093","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}
Lanfei Lu, Yu Li, Chenxiaoning Meng, Kunyu Liu, Yue Yu, Hui Chen, Guoming Liu, Yang Wang
{"title":"Single Catalyst with Dynamic Ligands Enabled Synthesis of Olefin Block Copolymers","authors":"Lanfei Lu, Yu Li, Chenxiaoning Meng, Kunyu Liu, Yue Yu, Hui Chen, Guoming Liu, Yang Wang","doi":"10.1021/jacs.4c18606","DOIUrl":"https://doi.org/10.1021/jacs.4c18606","url":null,"abstract":"Olefin block copolymers (OBCs) are among the most advanced classes of polyolefins, produced in large quantities as part of the approximately 200 million tons of polyolefins produced annually. However, current OBCs manufacturing relies on a complex, costly, two-catalyst process that requires hazardous chain shuttling agents. A more efficient approach using a single catalyst for the synthesis of the OBCs is highly desirable but remains significantly challenging. Traditional olefin copolymerization catalysts typically grow a single polymer chain and are incapable of generating block structures as they fail to incorporate α-olefins with the necessary precision. To achieve block copolymerization, the catalyst must simultaneously accomplish two seemingly contradictory tasks, efficiently and inefficiently incorporating α-olefins into the polymer chain. Here, we introduce a new approach for synthesizing OBCs using a single catalyst. By coupling this catalyst with a regulating agent, we enabled a one-step synthesis of OBCs with tunable hard/soft block ratios and high melting temperatures (∼120 °C). This method offers significant advantages, featuring its operational simplicity, elimination of chain shuttling agents, separate comonomer addition, or adjustments in reaction conditions. Mechanistic studies suggest that alkyl chains act as temporary ligands, dynamically influencing the catalyst’s polymerization behavior. This dynamic process allows the catalyst to alternate between efficient and inefficient α-olefin incorporators, thereby facilitating the synthesis of OBCs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814350","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}