Journal of the American Chemical Society最新文献

{"title":"Effective Near-Infrared Triplet Emitter Based on Hetero-Metal–Metal Interaction","authors":"Ning Zhou, Yangbo Zhang, Xiong Wang, Peng Yang, Wei Lu, Qingyun Wan","doi":"10.1021/jacs.5c04585","DOIUrl":"https://doi.org/10.1021/jacs.5c04585","url":null,"abstract":"Incorporating metal–metal (M–M) interactions into excited states of closed-shell d⁸ and d¹⁰ metal complexes is an effective strategy in the design of near-infrared (NIR) phosphorescent materials. While extensive studies have focused on homometallic M-M-bonded excited states, the potential of heterometallic interactions remains relatively underexplored. Herein, we report a series of heterometallic Rh(I)–Pt(II) double salt complexes that achieve efficient NIR phosphorescence, with emission peak energy spanning 830–980 nm and room-temperature quantum yield up to 23%. In this system, the Rh(I) center lowers the emission energy, while the Pt(II) center enhances spin–orbit coupling (SOC) via its heavy-atom effect. The resulting materials exhibit an outstanding waveguiding performance in the NIR spectral region. Combined spectroscopic and time-dependent density functional theory (TDDFT) analyses reveal that the Rh(I)–Pt(II) interaction directly modulates the excited state character, enhancing the radiative decay while suppressing nonradiative decay pathways. This work establishes heterometallic M–M cooperativity as a design principle for high-performance NIR phosphorescence, opening avenues for tailored NIR phosphorescent materials beyond conventional homometallic frameworks.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153918","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":"Fluorescence Visualization of Strain by Tetraphenylethylene/Ruthenium Complex Three-Dimensional Covalent Organic Framework Assemblies","authors":"Yingying Ren, Wenze Wu, Yuxuan Lu, Jiwei Li, Yang Liu, Haiqiang Jin, Xiaoyi Li, Xiaozhong Qu, Zhenzhong Yang","doi":"10.1021/jacs.5c05354","DOIUrl":"https://doi.org/10.1021/jacs.5c05354","url":null,"abstract":"Dynamic visualization of strain and its distribution in materials are still challenging. Herein, dual-fluorophore three-dimensional covalent organic frameworks (3D-COFs) and the PEGylated 3D-COFs (PEG-3D-COFs) were synthesized for the construction of physically interacted assemblies to realize fluorescence imaging on not only strain distribution but also strain-related surface friction and flow velocity distributions in various media including polymer elastomers, organic or aqueous dispersions. The responsiveness arises from the controllability of the aggregation structure of 3D-COFs and PEG-3D-COFs, showing concentration-dependent morphology and photoluminescence, and meanwhile having a concentration-deformation equivalence on the structural evolution dynamics which drives the color change of the COF emission in the solids and liquids with high sensitivity and reversibility, whenever the superstructure of the COF assemblies is affected by the applied strain on the matrices. The report will inspire further efforts to construct responsive COFs for optical measurement aims.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"3 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153920","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":"Molecular Steganography Using Multistate Photoswitchable Hydrazones","authors":"Brandon Balamut, Ivan Aprahamian","doi":"10.1021/jacs.5c03668","DOIUrl":"https://doi.org/10.1021/jacs.5c03668","url":null,"abstract":"The development of photochromic compounds that can have multiaddressable and -stable states is desirable for imparting multistate responses in soft materials. Here, we report on two such photochromes, composed of <i>para</i>-NO₂- and pentafluoro-phenyl functionalized hydrazones connected nonsymmetrically through an isosorbide linker, which exhibit highly efficient, orthogonal, and sequential switching. We took advantage of these properties and the multistability of the four different isomeric states (i.e., <i>ZZ</i>, <i>ZE</i>, <i>EZ</i>, and <i>EE</i>) to control the photophysical properties of nematic liquid crystals (LCs). Doping the switches into 5CB, followed by switching to the <i>EE</i> state, triggered an unusual cholesteric to focal conic phase transition. We used this property to modulate the opacity of the LC films, resulting in a molecular steganography application.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"5 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154296","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":"Piercing Molecular Graphenes: Precision Synthesis and Photophysics of NBN-Edged Porous Molecular Carbons","authors":"Yang Yu, Asier Izu, José M. Marín Beloqui, Shammi Rana, Kunal S. Mali, Steven De Feyter, David Casanova, Juan Casado, Junzhi Liu","doi":"10.1021/jacs.5c06175","DOIUrl":"https://doi.org/10.1021/jacs.5c06175","url":null,"abstract":"Bottom-up solution-phase synthesis of atomically precise porous nanographenes is a challenging endeavor. In particular, molecular carbons with multiple pores and heteroatoms remain unknown. Herein, we report three porous molecular carbons (<b>2PNG</b>, <b>3PNG</b>, and <b>7PNG</b>) with precise NBN-doped zigzag edges, in which <b>7PNG</b> possesses seven pores. X-ray crystallographic diffraction and scanning tunneling microscopy reveal their unique pore structures and self-assembly behaviors. Interestingly, the HOMO–LUMO overlap of these molecules gradually decreases as the size of the molecule increases, which induces peripheral-to-core excitations and promotes intersystem crossing. Steady-state and transient spectroscopy, along with DFT calculations, reveal the excited-state dynamics and the size-dependent energy-transfer mechanism in these NBN-doped molecular systems. Our study describes a new strategy for producing minimal wave function overlaps at almost planar geometry by segmenting the electronic structures of molecular graphene by insertion of pores, forcing the excitation to occur between the periphery and the core, with great potential for new phosphorescent and delayed fluorescence emitters.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153922","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":"Crystallographic Visualization of Distinct Iodic Aggregations in Isostructural Metal–Organic Frameworks","authors":"Yi Han, Yiwen He, Yin-Ke Fu, Hongliang Huang, Hongdong Li, Jiong-Peng Zhao, Lei Wang, Qian Niu, Nathaniel L. Rosi","doi":"10.1021/jacs.5c04910","DOIUrl":"https://doi.org/10.1021/jacs.5c04910","url":null,"abstract":"Precisely determining the location of adsorbed molecules is essential for illuminating the mechanisms underlying molecular confinement within porous metal–organic frameworks (MOFs). Here, we present the pore-filling and reactive adsorption of iodine in ALP-MOF-1 and its isostructural redox-active ALP-MOF-2. The adsorbed iodine molecules (I₂) are unaffected by Zn(II) in ALP-MOF-1 and are exclusively confined into an unusual three-dimensional (3D) iodine aggregation due to the 3D cross-linked pore topology and multiple I₂-framework interactions. Conversely, in ALP-MOF-2, the adsorbed I₂ enables the oxidation of Co(II) to Co(III), which is accompanied by the reduction of I₂ to I₃^– and the formation of I₅^– and I₂ during continuous I₂ loading. Identification of distinct iodine adsorption processes in ALP-MOF-1 and −2 motivated tuning of the metal ion composition to adjust the adsorption mechanism. The iodic aggregations in both MOFs are unambiguously confirmed by the combination of single crystal X-ray diffraction and spectroscopic characterization. The presence of multiple adsorption sites facilitate rapid iodine uptake of ∼179 wt % in ALP-MOF-1 and ∼150 wt % in ALP-MOF-2 within ∼5 h, which could be advantageous for applications requiring rapid and energy-efficient iodine capture.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153919","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":"Fully Conjugated Thiophene-Fused Oligo-BODIPYs: A Class of Intensely Near-Infrared Absorbing, Arc-Shaped Materials with up to 31 Linearly-Fused Rings","authors":"Qingbao Gong, Jinsong Shao, Wanwan Li, Xing Guo, Shizhang Ling, Yun Wu, Yaxiong Wei, Xinsheng Xu, Xiaochun Jiang, Lijuan Jiao, Erhong Hao","doi":"10.1021/jacs.5c05873","DOIUrl":"https://doi.org/10.1021/jacs.5c05873","url":null,"abstract":"Structurally well-defined large π-conjugated systems attract significant interest in molecular materials both for their unique electronic/photophysical properties and unexplored structure–property relationships arising from synthetic challenges. Herein, we address this challenge by leveraging a series of polycondensed π-system doping with B, N and S heteroatoms. In our approach, a series of fully conjugated thiophene-fused oligo-BODIPYs with atomic precision have been efficiently synthesized through the combination of intermolecular S_NAr reactions followed by intramolecular aromatic oxidative couplings from halogenated BODIPY precursors. The largest architecture is a fully fused BODIPY octamer, featuring a coplanar backbone of 31 linearly fused rings. The extended π-conjugation causes a dramatic shift of the absorption event from about 500 nm (monomer) to 822 nm (octamer) with extremely high molar absorptivities reaching 800,000 M^–1 cm^–1, as well as maintaining intense fluorescence intensity (Φ_FL up to 0.32), long triplet lifetime (τ_T = 0.61–15.4 μs), efficient triplet quantum yields (Φ_T = 0.24–0.81) and good singlet oxygen generation abilities. More interestingly, due to the weak aromaticity of thiophene, oligo-BODIPYs exhibit triplet state localization as their conjugation length increases, where the triplet energy remains constant while the singlet energy decreases significantly. Notably, intense near-infrared thermally activated delayed fluorescence (TADF) is observed even in tetramers, hexamers, and octamers. Our findings not only present a new series of heteroatom-doped condensed π-systems but also establish a precise regulation mechanism for singlet–triplet energy levels in molecules with large rigid π-conjugated structures. Furthermore, this work provides a novel strategy for designing next-generation TADF molecules with narrowband emission.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153921","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":"Amplification of Asymmetry for Dynamic Helical Polymers through 1:1 Host–Guest Interactions: Theoretical Models for Majority Rule and Sergeants and Soldiers Effects","authors":"Nozomu Suzuki, Daisuke Taura, Yusuke Furuta","doi":"10.1021/jacs.5c03406","DOIUrl":"https://doi.org/10.1021/jacs.5c03406","url":null,"abstract":"Amplification of asymmetry (chiral amplification) is one of the distinctive phenomena of dynamic helical polymers whose helical sense excess is significantly enhanced with a small amount of chiral units through the strong cooperative interactions among the monomer units. The Ising model for the amplification of asymmetry in the dynamic helical copolymers bearing the chiral side chains has been well-established. However, the theoretical models have not yet been developed for the amplification of asymmetry in the dynamic helical polymers induced by noncovalent intermolecular (host–guest) interactions of the achiral side chains with the chiral/chiral (majority rule effect) and chiral/achiral (sergeants and soldiers effect) guest molecules. In this work, we propose the theoretical models for two types of 1:1 host–guest interactions: the majority rule effect type 1:1 host–guest interaction (MRHG) and sergeants and soldiers effect type 1:1 host–guest interaction (SSHG) models, in which each twisting unit of the dynamic helical polymers is assumed to interact with one guest molecule. The excess energy of the helical reversal state (Δ<i>G</i>_r), per unit energy favoring one helical state over the other (2Δ<i>G</i>_h), and enantioselectivity (α) can be effectively determined using the MRHG model. Moreover, it was revealed that the chiral solvation model reported by Green, Morawetz, and co-workers is a particular solution of the SSHG model.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154295","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":"Tailoring Chloride Solid Electrolytes for Reversible Redox","authors":"Phillip Ridley, George Duong, Sarah L. Ko, Jin An Sam Oh, Grayson Deysher, Kent J. Griffith, Ying Shirley Meng","doi":"10.1021/jacs.4c14670","DOIUrl":"https://doi.org/10.1021/jacs.4c14670","url":null,"abstract":"Solid-state electrolytes enable next-generation batteries that can theoretically deliver higher energy densities while improving device safety. However, when fabricating cathodes for all-solid-state batteries, solid-state electrolytes must be combined with the active materials in high weight fractions in order to achieve sufficient ionic percolation within the cathode composite. This requirement drastically hinders the practicality of solid-state batteries as the solid-state electrolyte is conventionally designed to be electrochemically inactive and is effectively electrochemical “dead weight”, lowering both the gravimetric and volumetric energy density of the cell. In this work, a well-known solid-state electrolyte, Na₂ZrCl₆, is modified by aliovalent substitution of inactive Zr⁴⁺ cations with redox-active <i>M</i>⁵⁺ (<i>M</i> = Nb or Ta) cations to create a series of Na_2–<i>x</i><i>M</i>_<i>x</i>Zr_1–<i>x</i>Cl₆ solid solutions that possess both high ionic conductivities and active sites for Na⁺ storage. The Na⁺ intercalation mechanisms of these solid-solution materials, in addition to those of the Na<i>M</i>Cl₆ end-member materials, are elucidated in this work. It was discovered that both the niobium- and tantalum-containing chlorides exhibit rather high electrochemical potentials (2.2–2.8 V vs Na₉Sn₄), making them ideal catholytes to pair with commonly used oxide cathode materials like NaCrO₂. This synergistic pairing leads to a cathode composite with an 83–102% increase in energy density and 39–81% improvement in areal discharge capacity compared to a redox-innocent solid electrolyte. This approach highlights the benefits of designing and employing redox-active solid-state electrolytes that can reversibly intercalate charge-carrying cations, opening up a broad new avenue for solid-state electrolyte discovery and solid-state battery design.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"59 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154294","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":"Electrical Detection of Magnetic Perturbations through the Magnetoelectric Effect of a Molecular Spin Triangle","authors":"Balwant Singh Chauhan, Ratnamala Chatterjee, Philippe Turek, Athanassios K. Boudalis","doi":"10.1021/jacs.5c05601","DOIUrl":"https://doi.org/10.1021/jacs.5c05601","url":null,"abstract":"Dielectric and magnetoelectric (ME) studies were conducted on polycrystalline samples of the molecular spin triangle [Fe₃O(O₂CPh)₆(py)₃]ClO₄·py (<b>Fe</b>_<b>3</b>) and on its diamagnetic isostructural Ga^III analogue (<b>Ga</b>_<b>3</b>). Dielectric studies revealed a thermally activated process between approximately 15–60 K, attributed to the freezing-unfreezing of the crystallographically disordered pyridine solvates, with a paraelectric behavior above ∼68 K. Magnetoelectric studies revealed a second-order ME effect for <b>Fe</b>_<b>3</b>, which remained significant above liquid-nitrogen temperatures. Similar experiments on <b>Ga</b>_<b>3</b> allowed to control for the instrumental baseline response and to confirm the origin of the signal as the ME effect of <b>Fe</b>_<b>3</b>. The thermal evolution of the ME coupling coefficient (α_ME) showed no discontinuities around the temperature of the freezing–unfreezing processes, indicating that it is unrelated to them. These latter are assigned the disordered-diamagnetic sublattice consisting of the pyridine solvates and perchlorate counteranions. In turn, the ME coupling is assigned to the ordered-magnetic sublattice consisting of the <b>Fe</b>_<b>3</b> trinuclear cations. These results demonstrate that <b>Fe</b>_<b>3</b> can directly transform magnetic perturbations to electric signals at the single-molecule level, without the need of structural transformations or long-range magnetic ordering.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"36 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154174","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":"Kinetic Dissection of Proton-Coupled Conformational Transitions in Nucleic Acids by Integrating pH-Dependent NMR and Chemical Modifications.","authors":"Yeongjoon Lee,Rohit Roy,Stephanie Gu,Subin B Shetty,Atul K Rangadurai,Hashim M Al-Hashimi","doi":"10.1021/jacs.5c01663","DOIUrl":"https://doi.org/10.1021/jacs.5c01663","url":null,"abstract":"Proton-coupled conformational transitions play fundamental roles in nucleic acid recognition, catalysis, and folding, yet the kinetic mechanisms underlying these multistep protonation reactions remain unknown. Here, we present an approach to resolve the dominant kinetic pathway and rate-limiting step, which combines NMR chemical exchange measurements with chemical perturbations that shift pKa or modulate conformational equilibria. Applying the approach to three nucleic acid systems, we find the microscopic protonation step to be a diffusion-limited proton transfer reaction (kprot ∼ 1011 M-1 s-1), 2 orders of magnitude faster than diffusion-limited ligand-binding. For an A+-C mismatch in duplex DNA, protonation was the rate-limiting step occurring after the conformational change at a diffusion-limited kon ∼ 1011 M-1 s-1 via conformational selection of the wobble conformation, which forms rapidly and in significant abundance in the neutral ensemble. In RNA, the A-C wobble was sparsely populated in the neutral ensemble. The apparent kon was 2 orders of magnitude slower, and the reaction followed an induced-fit mechanism, where the unpaired adenine was initially protonated, followed by rate-limiting intrahelical flipping. The apparent kon was 5 orders of magnitude slower for the protonated G(syn)-C+ Hoogsteen conformation in duplex DNA in which cytosine protonation was rate-limiting occurring after the conformational change via conformational selection of an energetically disfavored G(syn)-C intermediate. These kinetic models quantitatively predicted the impact of pH shifts and chemical modifications on reaction kinetics. Our findings reveal how differences in nucleic acid conformational ensembles can drive diverse kinetic responses to pH changes and chemical modifications, even in binding reactions involving the simplest ligand: the proton.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"239 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146239","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}