Journal of the American Chemical Society最新文献_第9页

Structural Modulation and Enhanced Magnetic Ordering in Incommensurate K_1-xCrSe₂ Crystals.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-30 DOI: 10.1021/jacs.4c13545

Felix Eder, Catherine Witteveen, Enrico Giannini, Fabian O von Rohr

{"title":"Structural Modulation and Enhanced Magnetic Ordering in Incommensurate K1-xCrSe2 Crystals.","authors":"Felix Eder, Catherine Witteveen, Enrico Giannini, Fabian O von Rohr","doi":"10.1021/jacs.4c13545","DOIUrl":"10.1021/jacs.4c13545","url":null,"abstract":"Layered delafossite-type compounds and related transition metal dichalcogenides, characterized by their triangular net structures, serve as prototypical systems for exploring the intricate interplay between crystal structure and magnetic behavior. Herein, we report on the discovery of the compound K1-xCrSe2 (x ≈ 0.13), an incommensurately modulated phase. Single crystals of this compound were grown for the first time using a K/Se self-flux. We find a monoclinic crystal structure with incommensurate modulation that can be rationalized by a 3 + 1-dimensional model. This modulation compensates for the under-stoichiometry of K cations, creating pronounced undulations in the CrSe2 layers. Our anisotropic magnetization measurements reveal that K1-xCrSe2 undergoes a transition to a long-range magnetically ordered state below TN = 133 K, a temperature 1.6 to 3.3 times higher than in earlier reported KCrSe2 compounds. Our findings open new avenues for tuning the magnetic properties of these layered materials through structural modulation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"4896-4903"},"PeriodicalIF":14.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062440","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

Half-Sandwich Ru(II) Complexes Featuring Metal-Centered Chirality: Configurational Stabilization by Ligand Design, Preparation via Kinetic Resolution, and Application in Asymmetric Catalysis

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 DOI: 10.1021/jacs.4c16928

Hui Liang, Gabriel N. Morais, Gang Chen, Wei Tang, Jing Zhao, Chuanyong Wang, K. N. Houk, Shuming Chen, Jiajia Ma

{"title":"Half-Sandwich Ru(II) Complexes Featuring Metal-Centered Chirality: Configurational Stabilization by Ligand Design, Preparation via Kinetic Resolution, and Application in Asymmetric Catalysis","authors":"Hui Liang, Gabriel N. Morais, Gang Chen, Wei Tang, Jing Zhao, Chuanyong Wang, K. N. Houk, Shuming Chen, Jiajia Ma","doi":"10.1021/jacs.4c16928","DOIUrl":"https://doi.org/10.1021/jacs.4c16928","url":null,"abstract":"While it is well established that half-sandwich Ru(II) complexes possess metal-centered chirality, effective strategies to leverage their metal-centered chirality toward asymmetric synthesis have been challenging due to the configurational lability of the metal stereocenters. The metal-centered chirality is typically mediated by enantiopure ligands, which occupy a relatively narrow chemical space compared to their achiral counterparts. We demonstrate that achiral ligands can be used to access chiral-at-ruthenium half-sandwich complexes with exceptionally high configurational stability. Key to success is the introduction of a rigid bidentate ligand with a minimized dihedral angle between the pyridyl and phenolic moieties, which proved effective for preventing racemization. Computational studies revealed the energetic factors contributing to the exceptional configurational stability enabled by the rigid and planar structure of the successful ligand design. These optically active chiral-at-ruthenium complexes incorporating aldehyde moieties were obtained by NHC-catalyzed kinetic resolution with excellent selectivities (s-factor up to >200, ee up to 99%). We further demonstrate that they are highly effective chiral aldehyde catalysts for the asymmetric 1,6-conjugate addition of glycine ester and para-quinone methide.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"63 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401991","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

Pd₁Ni₂ Trimer Sites Drive Efficient and Durable Hydrogen Oxidation in Alkaline Media.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-30 DOI: 10.1021/jacs.4c17605

Shu-Qi Wang, Ze-Cheng Yao, Zhuo-Qi Shi, Xuerui Liu, Tang Tang, Hai-Rui Pan, Lirong Zheng, Qinghua Zhang, Dong Su, Zhongbin Zhuang, Lu Zhao, Qi An, Jin-Song Hu

{"title":"Pd1Ni2 Trimer Sites Drive Efficient and Durable Hydrogen Oxidation in Alkaline Media.","authors":"Shu-Qi Wang, Ze-Cheng Yao, Zhuo-Qi Shi, Xuerui Liu, Tang Tang, Hai-Rui Pan, Lirong Zheng, Qinghua Zhang, Dong Su, Zhongbin Zhuang, Lu Zhao, Qi An, Jin-Song Hu","doi":"10.1021/jacs.4c17605","DOIUrl":"10.1021/jacs.4c17605","url":null,"abstract":"Anion-exchange membrane fuel cell (AEMFC) is a cost-effective hydrogen-to-electricity conversion technology under a zero-emission scenario. However, the sluggish kinetics of the anodic hydrogen oxidation reaction (HOR) impedes the commercial implementation of AEMFCs. Here, we develop a Pd single-atom-embedded Ni3N catalyst (Pd1/Ni3N) with unconventional Pd1Ni2 trimer sites to drive efficient and durable HOR in alkaline media. Integrating theoretical and experimental analyses, we demonstrate that dual Pd1Ni2 sites achieve a \"*H on Pd1Ni2-HV + *OH on Pd1Ni2-HN\" adsorption mode, effectively weakening the overstrong *H and *OH adsorptions on pristine Ni3N. Owing to the unique coordination mode and atomically dispersed catalytic sites, the resulting Pd1/Ni3N catalyst delivers a high intrinsic and mass activity together with excellent antioxidation capability and CO tolerance. Specifically, the HOR mass activity of Pd1/Ni3N reaches 7.54 A mgPd-1 at the overpotential of 50 mV. The AEMFC employing Pd1/Ni3N as the anode catalyst displays a high power density of 31.7 W mgPd-1 with an ultralow anode precious metal loading of only 0.023 mgPd cm-2. This study provides guidance for the design of high-performance alkaline HOR catalytic sites at the atomic level.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"5398-5407"},"PeriodicalIF":14.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062414","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

Atomic-Level Tin Regulation for High-Performance Zinc-Air Batteries.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-30 DOI: 10.1021/jacs.4c12601

Yunrui Li, Jiaqi Xu, Fan Lan, Yao Wang, Hairong Jiang, Ping Zhu, Xueke Wu, Ya Huang, Run Li, Qinyuan Jiang, Yanlong Zhao, Ruina Liu, Longgui Zhang, Rufan Zhang

{"title":"Atomic-Level Tin Regulation for High-Performance Zinc-Air Batteries.","authors":"Yunrui Li, Jiaqi Xu, Fan Lan, Yao Wang, Hairong Jiang, Ping Zhu, Xueke Wu, Ya Huang, Run Li, Qinyuan Jiang, Yanlong Zhao, Ruina Liu, Longgui Zhang, Rufan Zhang","doi":"10.1021/jacs.4c12601","DOIUrl":"10.1021/jacs.4c12601","url":null,"abstract":"The trade-off between the performances of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) presents a challenge in designing high-performance aqueous rechargeable zinc-air batteries (a-r-ZABs) due to sluggish kinetics and differing reaction requirements. Accurate control of the atomic and electronic structures is crucial for the rational design of efficient bifunctional oxygen electrocatalysts. Herein, we designed a Sn-Co/RuO2 trimetallic oxide utilizing dual-active sites and tin (Sn) regulation strategy by dispersing Co (for ORR) and auxiliary Sn into the near-surface and surface of RuO2 (for OER) to enhance both ORR and OER performances. Both theoretical calculations and advanced dynamic monitoring experiments revealed that the auxiliary Sn effectively regulated the atomic/electronic environment of Ru and Co dual-active sites, which optimized the *OOH/*OH adsorption behavior and promoted the release of the final products, thus breaking the reaction limits. Therefore, the as-designed Sn-Co/RuO2 catalysts exhibited superb bifunctional performance with an oxygen potential difference (ΔE) of 0.628 V and negligible activity degradation after 200,000 (ORR) or 20,000 (OER) CV cycles. The a-r-ZABs based on the Sn-Co/RuO2 catalyst exhibited a higher performance at a wide temperature range of -30 to 65 °C. They demonstrated an ultralong lifespan of 138 days (20,000 cycles) at 5 mA cm-2, 39.7 times higher than that of Pt/C + IrO2 coupled catalysts at a low temperature of -20 °C. Additionally, they maintained an initial power density of 85.8% after long-term tests, significantly outperforming previously reported catalysts. More importantly, the a-r-ZABs also showed excellent stability of 766.45 h (about 4598 cycles) at a high current density of 10 mA cm-2.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"4833-4843"},"PeriodicalIF":14.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062340","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

Ionic Remote α-C-H Allenylation of Silyl Ethers Involving a [1,5]-Hydride Shift Promoted by Silylium-Ion Regeneration.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-31 DOI: 10.1021/jacs.4c18137

Honghua Zuo, Sebastian Kemper, Hendrik F T Klare, Martin Oestreich

引用次数: 0

Superacid In Situ Protected Synthesis of Covalent Organic Frameworks

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 DOI: 10.1021/jacs.4c17548

Xingyao Ye, Ruoyang Liu, Xinyu Mu, Shanshan Tao, Hao Yang, Xuejiao J. Gao, Shuo-Wang Yang, Donglin Jiang

{"title":"Superacid In Situ Protected Synthesis of Covalent Organic Frameworks","authors":"Xingyao Ye, Ruoyang Liu, Xinyu Mu, Shanshan Tao, Hao Yang, Xuejiao J. Gao, Shuo-Wang Yang, Donglin Jiang","doi":"10.1021/jacs.4c17548","DOIUrl":"https://doi.org/10.1021/jacs.4c17548","url":null,"abstract":"Covalent organic frameworks, as a class of fascinating crystalline porous materials, are attracting increasing attention in various fields. Synthesizing these materials to attain crystallinity and porosity is essential; however, it is time-consuming, not cost-effective, and energy-demanding as it involves extensive screenings of reaction conditions and employs undesired aromatic solvents. Despite recent progress in the synthesis, finding an efficient, convenient, low-toxicity, and widely applicable method remains a challenging goal. Here, we report an in situ-protected strategy for synthesizing imine-linked frameworks by exploring triflic acid as the catalyst to replace traditional acetic acid and deploying alcohols as a single-component reaction medium instead of aromatic solvents. We found that the function of triflic acid is threefold: it rapidly protonates amino groups of amine monomers into ammonium cations, protects formyl units of aldehyde monomers by converting them into acetals, and improves the solubilities of both monomers. The in situ-protection scheme greatly changes their concentrations and reactivities, making reactions highly controllable and reversible. This strategy is general for various monomer combinations to develop imine-linked frameworks with different topologies, including tetragonal, rhombic, pentagonal, hexagonal, kagome, dual trigonal, dual rhombic, and dual hexagonal shapes, and various pore sizes from micropores to mesopores, presenting a facile and simple way to synthesize 28 different yet high-quality frameworks in n-butanol/water. Remarkably, nine new imine-linked frameworks are synthesized for the first time, which cannot be prepared by traditional systems. The porphyrin frameworks exhibited exceptional photocatalytic activities in the activation of molecular oxygen to produce highly reactive oxygen species of singlet oxygen.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"47 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393841","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

Harnessing Oxidized Amines as Robust Sorbents for Carbon Capture

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 DOI: 10.1021/jacs.4c16764

Sijing Meng, Tristan H. Lambert, Phillip J. Milner

{"title":"Harnessing Oxidized Amines as Robust Sorbents for Carbon Capture","authors":"Sijing Meng, Tristan H. Lambert, Phillip J. Milner","doi":"10.1021/jacs.4c16764","DOIUrl":"https://doi.org/10.1021/jacs.4c16764","url":null,"abstract":"Carbon capture and sequestration (CCS) is imperative to mitigating global climate change, but current implementation falls far short of that needed to reach net-zero global emissions by 2050. Aqueous amine solutions, conceived over a century ago, are the current leading technology for CO2 separations. However, amines suffer from chemical instability under scrubbing conditions, corrosiveness, and toxicity, hindering their long-term implementation at multiton scales. Herein, we demonstrate for the first time that tertiary amine N-oxides, an oxidative degradation product of amines, can remove CO2 from dilute streams, including flue gas from a natural gas-fired power plant. Our extensive spectroscopic and computational studies support that the nontoxic, noncorrosive, and inexpensive 4-methylmorpholine N-oxide (MMNO) captures CO2 under humid conditions via the formation of a hydrogen-bond-stabilized bicarbonate (HCO3–) species, despite being significantly less basic than an amine. Accelerated aging studies show that MMNO exhibits superior oxidative and thermal stability compared to structurally similar amines, highlighting the potential of eco-friendly N-oxides in industrial carbon capture applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"63 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393843","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

N-Protonated Acridinium Catalyst Enables Anti-Markovnikov Hydration of Unconjugated Tri- and Disubstituted Olefins.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-31 DOI: 10.1021/jacs.4c18185

Boris Alexander van der Worp, Tobias Ritter

引用次数: 0

Photolytic and Thermal Reactions of [C₆H₄(PPh₂)₂(μ-N₂)] and Its Lewis Acid Adducts: N-N Bond Cleavage and Liberation of N₂.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-30 DOI: 10.1021/jacs.4c16123

Linkun Miao, Jason Yeung, Amir Yeganeh-Salman, Zheng-Wang Qu, Stefan Grimme, Douglas W Stephan

引用次数: 0

Sulfur Lone Pairs Open Avenues for π* → n Orange-to-Red TADF and OLEDs.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-01-30 DOI: 10.1021/jacs.4c18235

Hao Sun, Xuping Li, Chao-Hsien Hsu, Chieh-Ming Hung, Bin Wu, Zhe-Hong Su, Glib V Baryshnikov, Chenzi Li, Hans Ågren, Zhiyun Zhang, Wei Huang, Dayu Wu, Pi-Tai Chou, Liangliang Zhu

{"title":"Sulfur Lone Pairs Open Avenues for π* → n Orange-to-Red TADF and OLEDs.","authors":"Hao Sun, Xuping Li, Chao-Hsien Hsu, Chieh-Ming Hung, Bin Wu, Zhe-Hong Su, Glib V Baryshnikov, Chenzi Li, Hans Ågren, Zhiyun Zhang, Wei Huang, Dayu Wu, Pi-Tai Chou, Liangliang Zhu","doi":"10.1021/jacs.4c18235","DOIUrl":"10.1021/jacs.4c18235","url":null,"abstract":"It is always important and fascinating to explore new organic emitters that exploit unconventional pathways to unveil their emission with unique properties, such as thermally activated delayed fluorescence (TADF). In this study, we report that the rarely explored sulfur lone pair (n) is a promising alternative, where the correlated π* → n emission can be used to attain strong TADF and thus practical OLEDs. The designed strategy incorporates several key concepts (Figure 1a), in which the persulfide aromatic spirocycle enhances spin-orbit coupling, thereby increasing the intersystem crossing rate. Next, molecules with a twisted donor-acceptor configuration bridged by spiro[4.4]nonane as well as spatially orthogonal sulfur lone pairs and π* features significantly reduce the singlet-triplet gap. Finally, the rigid spirocyclic backbone inhibits nonradiative transitions. The proof-of-concept is given by compound 1, which achieves nπ* thermally activated delayed fluorescence (TADF) maximized at 635 nm with photoluminescence quantum yields as high as 52% in CH2Cl2. Wet-processed OLEDs containing 1 achieved a maximum external quantum efficiency of 6.4% at a brightness of 189 cd m-2 (∼600 nm), opening an alternative 1nπ* route for practical π* → n TADF OLEDs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"5432-5439"},"PeriodicalIF":14.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062442","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