Journal of the American Chemical Society最新文献

{"title":"Dynamic Competition between Hubbard and Superexchange Interactions Selectively Localizes Electrons and Holes through Polarons","authors":"Jocelyn L. Mendes, Hyun Jun Shin, Jae Yeon Seo, Nara Lee, Young Jai Choi, Joel B. Varley, Scott K. Cushing","doi":"10.1021/jacs.4c16837","DOIUrl":"https://doi.org/10.1021/jacs.4c16837","url":null,"abstract":"Controlling the effects of photoexcited polarons in transition metal oxides can enable the long time-scale charge separation necessary for renewable energy applications and controlling new quantum phases through dynamically tunable electron–phonon coupling. In previously studied transition metal oxides, polaron formation is facilitated by a photoexcited ligand-to-metal charge transfer (LMCT). When the polaron is formed, oxygen atoms move away from iron centers, which increases carrier localization at the metal center and decreases charge hopping. Studies of yttrium iron garnet and erbium iron oxide have suggested that strong electron and spin correlations can modulate photoexcited polaron formation. To understand the interplay between strong spin and electronic correlations in highly polar materials, we studied gadolinium iron oxide (GdFeO₃), which selectively forms photoexcited polarons through an Fe–O–Fe superexchange interaction. Excitation-wavelength-dependent transient extreme ultraviolet (XUV) spectroscopy selectively excites LMCT and metal-to-metal charge transfer (MMCT) transitions. The LMCT transition suppresses photoexcited polaron formation due to the balance between superexchange and Hubbard interactions, while MMCT transitions result in photoexcited polaron formation within 250 ± 40 fs. Ab initio theory demonstrates that electron and hole polarons localize on iron centers following MMCT. In addition to understanding how strong electronic and spin correlations can control strong electron–phonon coupling, these experiments separately measure electron and hole polaron interactions on neighboring metal centers for the first time, providing insight into a large range of charge-transfer and Mott–Hubbard insulators.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901726","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":"Enhanced Intermediates Inter-migration on Ag Single-Atom Alloys for Boosting Multicarbon Product Selectivity in CO2 Electroreduction","authors":"Min Wang, Minghui Fang, Yingxuan Liu, Chunjun Chen, Yichi Zhang, Shuaiqiang Jia, Haihong Wu, Mingyuan He, Buxing Han","doi":"10.1021/jacs.5c03057","DOIUrl":"https://doi.org/10.1021/jacs.5c03057","url":null,"abstract":"Electrochemical CO₂ reduction reaction (CO₂RR) to multicarbon (C₂₊) products holds immense significance in promoting a closed carbon cycle and solving global energy problems, but it faces challenges of unsatisfactory selectivity. In this work, we constructed an Ag single-atom alloy cascade catalyst (AgCu-SAA) using an epoxide gelation approach, which enhanced the utilization efficiency of the CO intermediate through an inter-migration pathway. As a result, the C₂₊ products’ Faradaic efficiency (FE) of 83.4% was achieved at a current density of 900 mA cm^–2. Moreover, the FE of the C₂₊ products remained as high as 74.8% even at a high current density of 1100 mA cm^–2. In situ Raman spectra and density functional theory (DFT) calculations reveal that CO₂ is first converted to CO over the single-atom Ag site. Subsequently, the generated CO is directly transferred to the adjacent Cu site rather than desorbing into the electrolyte. This process avoids the inefficient migration of CO inter-mediates, thereby enhancing the selectivity for the formation of C₂₊ products.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"5 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898067","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":"Colocalized Raman and IR Spectroscopies via Vibrational-Encoded Fluorescence for Comprehensive Vibrational Analysis","authors":"Zhao-Dong Meng, Tai-Rui Wu, Li-Ling Zhou, En-Ming You, Zhi-Peng Dong, Xia-Guang Zhang, Gan-Yu Chen, De-Yin Wu, Jun Yi, Zhong-Qun Tian","doi":"10.1021/jacs.5c01957","DOIUrl":"https://doi.org/10.1021/jacs.5c01957","url":null,"abstract":"Vibrational spectroscopy, including Raman scattering and infrared (IR) absorption, provides essential molecular fingerprint information, facilitating diverse applications, such as interfacial sensing, chemical analysis, and biomedical diagnostics. The complementary selection rules of Raman and IR spectroscopies offer distinct, yet mutually reinforcing, insights into molecular structure and dynamics. However, in dynamic or complex chemical environments, either technique alone is not capable of providing a complete and nuanced picture of molecular vibrations. Simultaneous detection of complementary vibrational modes within the same molecular group remains challenging due to wavelength discrepancies and sensitivity mismatches between Raman and IR spectroscopies. In this work, to address the gap between these spectroscopies, we developed an integrated approach based on vibrational-encoded fluorescence (VEF), in which the complementary vibrational information is respectively encoded into the different parts of fluorescence radiation: Stokes fluorescence carrying Raman information and anti-Stokes fluorescence reflecting IR information. This method employs a dual-resonant microsphere-on-mirror plasmonic structure to bridge the waveband gap, enabling the simultaneous detection of complete vibrational modes in the visible spectrum with ultrahigh sensitivity down to ∼100 molecules. Hyperspectral colocalization imaging demonstrates spatial correlations between the complementary vibrations. By careful calibration, the detection efficiency is improved by 8 orders of magnitude compared to unenhanced IR spectroscopy. This approach creates new opportunities for the precise identification of molecular vibrational information in complex chemical environments.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901683","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":"Cathode–Anode Synergy Electrosynthesis of Propanamide via a Bipolar C–N Coupling Reaction","authors":"Ming-Hao Guan, Hao-Nan Xu, Jin Liu, Xiao-Ya Zhou, Tao Wu, An-Hui Lu","doi":"10.1021/jacs.5c01744","DOIUrl":"https://doi.org/10.1021/jacs.5c01744","url":null,"abstract":"Propanamide is a crucial synthetic intermediate in pharmaceuticals for the preparation of antibacterial and anticancer drugs. Conventional synthesis of propanamide involves the reaction of carboxylic acid derivatives with amines, which requires harsh reaction conditions, leading to an unfavorable environmental footprint. Here, we present a cathode–anode synergistic electrochemical strategy to transform nitrate and n-propanol into propanamide under ambient conditions, where both the cathode catalyst Co₃O₄/SiC and the anode catalyst Ti contribute distinctively to the electrochemical process. The CH₃CH₂CHO produced at the Ti anode can diffuse and react with the adsorbed intermediate *NH₂OH on the surface of the cathode catalyst to form propanamide. The synergistic reactions at both electrodes collectively enhance the efficiency of the propanamide synthesis. This design enables efficient propanamide production in a flow cell at the gram scale with a remarkable yield of 986.13 μmol/(cm²·h) at current densities of up to 650 mA/cm². Our reports present a new option for environmentally friendly C–N bond synthesis, and the insights can be useful for the electrosynthesis of a wider scope of amides.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898066","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":"Violations of Coordination: Exploring Metastable Diborides via Energetic Transition Metals","authors":"Joseph T. Doane, Gregory M. John, Alma Kolakji, Abraham A. Rosenberg, Yiren Zhang, Alan A. Chen, Michael T. Yeung","doi":"10.1021/jacs.5c04066","DOIUrl":"https://doi.org/10.1021/jacs.5c04066","url":null,"abstract":"The ideal aeronautical solid-state fuel should possess a high gravimetric heat of combustion (more energy for less weight) and a high volumetric heat of combustion (more room for mission-critical items). In this work, manganese diboride (MnB₂) demonstrates a high gravimetric heat of combustion of 39.26 kJ/g and the highest volumetric heat of combustion of any known fuel of 208.08 kJ/cm³. When compared to the currently used fuel in Space Shuttle rocket boosters and the Space Launch System, aluminum metal, MnB₂ represents a 26% increase in gravimetric heat of combustion and a 148% increase in volumetric heat of combustion. Surprisingly, the local topology of the inner coordination sphere controls energetic output. A model cluster system analyzed by density functional theory shows that the local environment can contribute to the bulk properties even without physical manifestations in the periodic structure. This high enthalpic performance comes from the metastability of MnB₂ and demonstrates that transition metals, typically shunned as solid-state fuels, can store potential energy from their high-temperature synthesis through ‘overcoordination’ and violation of their valence shell.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"70 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898069","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":"Regulating Amine Substitution in Fluorosulfonyl-Based Flame-Retardant Electrolytes for Energy-Dense Lithium Metal Batteries","authors":"Lan-Qing Wu, Zhe Li, Huamei Li, Jin-Yu Zhang, Yong Li, Shuang-Xin Ren, Zhen-Yu Fan, Xiao-Tian Wang, Kun Li, Zhen Liu, Jie Zhang, Ji-Chi Yang, Ya-Wen Li, Shou-Hang Bo, Qing Zhao","doi":"10.1021/jacs.5c03606","DOIUrl":"https://doi.org/10.1021/jacs.5c03606","url":null,"abstract":"Sulfone-based electrolytes offer unusually high anodic and thermal stability that in principle makes them promising candidates for fabricating energy-dense lithium metal batteries (LMBs). Their uses in practical batteries are currently limited by their inability to sustain long-term Li metal plating/stripping processes due to their high reactivity toward the Li metal. Here, we report on the design and synthesis of a unique family of fluorosulfonyl group-based (FSO₂^–) molecules, modified with ethyl (FSE)/<i>N</i>,<i>N</i>-dimethyl (FSNDM)/<i>N</i>,<i>N</i>-diethyl (FSNDE)/<i>N</i>-pyrrolidine (FSNP) end groups to create exceptionally stable single-salt single-solvent electrolytes. The flammability, solvation structure, ion transport, Li metal deposition kinetics, and high-voltage stability of the electrolytes are systematically studied. It is shown that the electrolytes are nonflammable, possess weak solvation characteristics, yet manifest high room-temperature ionic conductivities (1.6–6.1 mS cm^–1) and low solution viscosities. In comparison to FSE, the FSNDM-, FSNDE-, and FSNP-based electrolytes exhibit an exceptionally reversible Coulombic efficiency for Li metal plating/stripping (&gt;99.71% over 800 cycles) and exhibit typical oxidative stability at voltages exceeding 4.6 V. Deployed as electrolytes in Li metal batteries (20 μm Li anode and 3 g A h^–1 electrolyte) with high-loading (18.5 mg cm^–2) LiNi_0.8Co_0.1Mn_0.1O₂ cathodes, 329 cycles have been achieved before 80% capacity retention. Six Ah Li metal pouch cells based on the designed electrolytes also exhibit high stability and high energy density (496 W h kg^–1) for over 150 cycles with at most 2.7% volume expansion. Our findings demonstrate that through an intentional molecular design, sulfone electrolytes provide a robust route toward nonflammable Li metal compatible electrolytes with practical high-voltage cathodes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901729","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":"DNA-Based Networks Formed by Coordination Cross-Linking of DNA with Metal–Organic Polyhedra: From Gels to Aerogels to Hydrogels","authors":"Laura Hernández-López, Akim Khobotov-Bakishev, Alba Cortés-Martínez, Eduard Garrido-Ribó, Partha Samanta, Sergio Royuela, Félix Zamora, Daniel Maspoch, Arnau Carné-Sánchez","doi":"10.1021/jacs.5c03934","DOIUrl":"https://doi.org/10.1021/jacs.5c03934","url":null,"abstract":"Herein, we introduce a supramolecular method to form DNA-based networks by cross-linking DNA with Rh(II)-based metal–organic polyhedra (MOPs), which entails coordination of DNA to the exohedral Rh(II) axial sites of the MOP. The resultant highly connected networks can then be processed into gels, porous aerogels, or hydrogels, exhibiting properties suitable for pollutant removal and drug release.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898116","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":"Long-Range Resonant Charge Transport through Open-Shell Donor–Acceptor Macromolecules","authors":"Shaocheng Shen, Mehrdad Shiri, Paramasivam Mahalingam, Chaolong Tang, Tyler Bills, Alexander J. Bushnell, Tanya A. Balandin, Leopoldo Mejía, Haixin Zhang, Bingqian Xu, Ignacio Franco, Jason D. Azoulay, Kun Wang","doi":"10.1021/jacs.4c18150","DOIUrl":"https://doi.org/10.1021/jacs.4c18150","url":null,"abstract":"A grand challenge in molecular electronics is the development of molecular materials that can facilitate efficient long-range charge transport. Research spanning more than two decades has been fueled by the prospects of creating a new generation of miniaturized electronic technologies based on molecules whose synthetic tunability offers tailored electronic properties and functions unattainable with conventional electronic materials. However, current design paradigms produce molecules that exhibit off-resonant transport under low bias, which limits the conductance of molecular materials to unsatisfactorily low levels─several orders of magnitude below the conductance quantum 1 <i>G</i>₀─and often results in an exponential decay in conductance with length. Here, we demonstrate a chemically robust, air-stable, and highly tunable molecular wire platform comprised of open-shell donor–acceptor macromolecules that exhibit remarkably high conductance close to 1 <i>G</i>₀ over a length surpassing 20 nm under low bias, with no discernible decay with length. Single-molecule transport measurements and <i>ab initio</i> calculations show that the ultralong-range resonant transport arises from extended π-conjugation, a narrow bandgap, and diradical character, which synergistically enables excellent alignment of frontier molecular orbitals with the electrode Fermi energy. The implementation of this long-sought-after transport regime within molecular materials offers new opportunities for the integration of manifold properties within emerging nanoelectronic technologies.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893560","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":"Click Chemistry-Assisted Rejuvenation of Aging T Cells Sensitizes Aged Mice to Tumor Immunotherapy","authors":"Xue-Feng Bai, Jun-Chi Ma, Cheng Zhang, Zhu Chen, Jinlian He, Si-Xue Cheng, Xian-Zheng Zhang","doi":"10.1021/jacs.5c05312","DOIUrl":"https://doi.org/10.1021/jacs.5c05312","url":null,"abstract":"Enormous resources have been devoted to address the suboptimal response of tumor patients to immunotherapy. However, a crucial yet often overlooked factor in these effects is the strong correlation between the occurrence and development of tumors and the immune dysfunction associated with aging. Our study aims to rejuvenate aging T cells within tumor-draining lymph nodes (TdLNs) by using targeted delivery of rapamycin, a macrolide capable of mitigating aging-related decline in immune function, thereby enhancing the antitumor efficacy of immunotherapy in aged mice. The targeted delivery system relies on a bioorthogonal reaction that harnesses the click chemistry between the azide (N₃) groups artificially introduced onto TdLNs and the dibenzocyclooctyne (DBCO) groups attached to the rapamycin-loaded micelles administered intradermally. Experimental data demonstrate that this approach has effectively restored the functionality of impaired CD8⁺ T cells in aged mice, thereby enhancing the antitumor response to immune checkpoint blockade (ICB) therapy to levels comparable to those in young mice. This study presents a promising strategy to combat the resistance to immunotherapeutic approaches commonly encountered among elderly tumor patients.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893568","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":"Intrinsic Off-Centering and Light Conduction Band Structure Lead to High Thermoelectric Performance in N-Type Diamondoid AgInSe2","authors":"Jingyi Su, Yukun Liu, Yichen Li, Shulin Bai, Dezheng Gao, Pengpeng Chen, Zihao Zhao, Vinayak P. Dravid, Hongyao Xie, Li-Dong Zhao, Mercouri G. Kanatzidis","doi":"10.1021/jacs.5c04294","DOIUrl":"https://doi.org/10.1021/jacs.5c04294","url":null,"abstract":"Historically, the rocksalt crystal structure and its variants have long dominated the field of advanced thermoelectrics. Developing new structural thermoelectric materials is an interesting topic for the thermoelectric community. In this work, an n-type diamondoid compound, AgInSe₂, was identified with extremely low thermal conductivity and very high carrier mobility. The intrinsic Ag off-centering behavior combined with the densely distributed twin boundaries and switched grain orientations significantly disrupts phonon transport and leads to the extremely low thermal conductivity of ∼0.19 W m^–1 K^–1 at 850 K in the Ag_0.98In_1.02Se₂-0.03CdSe material. On the other hand, the light conduction band structure of AgInSe₂ leads to a small density-of-state effective mass of 0.1 <i>m</i>_e and very high electron mobility of 700 cm² V^–1 s^–1 at room temperature. Combining this with the significant increase in carrier concentration induced by CdSe alloying, a record-high maximum <i>ZT</i> of 1.4 at 850 K and an average <i>ZT</i> of 0.8 are achieved in n-type Ag_0.98In_1.02Se₂-0.03CdSe, which can be comparable to many typical rocksalt n-type thermoelectrics. Moreover, a maximum output power of ∼10 mW and an energy conversion efficiency of ∼5% were demonstrated in the AgInSe₂-based single-leg device, highlighting the application potential of this novel n-type diamondoid thermoelectric.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"15 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893566","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}