Journal of the American Chemical Society最新文献

{"title":"Convergent Total Synthesis of (−)-Methyl Gummiferolate Enabled by Pattern Recognition and Radical Cyclization","authors":"Weizhao Zhao,&nbsp;Jingsong Zhen,&nbsp;Mingji Dai","doi":"10.1021/jacs.6c15246","DOIUrl":"10.1021/jacs.6c15246","url":null,"abstract":"<p>We report herein an enantioselective total synthesisof (−)-methylgummiferolate, a complex diterpene natural product with a tetracyclic <em>ent</em>-atisane core including a bicyclo[2.2.2]octane subunitand three all-carbon quaternary centers. Gummiferolic acid has demonstratedpotent plant growth-regulatory activity similar or superior to gibberellicacid. Using pattern recognition analysis, the tetracyclic <em>ent</em>-atisane core of (−)-methyl gummiferolate wasretrosynthetically traced back to chiral pool molecule (<em>S</em>)-perillaldehyde and a six-membered ring containing starting materialwhich can be accessed using an enantioselective Diels–Alderreaction with the Rawal diene. Our forward synthesis features a substrate-controlledstereoselective MHAT-initiated Baran reductive olefin cross coupling(BROC), a powerful radical cyclization approach, to close the six-memberedB ring and an intramolecular alkylation to build the bicyclo[2.2.2]octanesubunit. The BROC precursor was assembled in a convergent manner usinga 1,2-addition of an alkyl lithium to a Weinreb amide derived from(<em>S</em>)-perillaldehyde. The alkyl lithium precursor wasprepared from a known cyclohexenone (<strong>12</strong>) using key stepsincluding CBS reduction, 2,3-Wittig–Still rearrangement, andAppel iodination. Overall, (−)-methyl gummiferolate was preparedin 18 steps from <strong>12</strong>.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"42898–42903"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149072769","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":"Confinement–Induced N2–Phobicity Enables O2 Extraction from Air for Catalysis","authors":"Jian Wang,&nbsp;Zhuoyang Xie,&nbsp;Li Li,&nbsp;Wei Ding,&nbsp;Zidong Wei","doi":"10.1021/jacs.6c15418","DOIUrl":"10.1021/jacs.6c15418","url":null,"abstract":"<p>Air is commonly used as an oxidizer in proton–exchangemembranefuel cells. However, only 20.9% of air is oxygen and approximately78% is nitrogen gas, which is inert and is often used to isolate oxygen.We report that N₂–phobicity together with confinement–catalysisexponentially increases the power density of H₂–airfuel cells by selectively transporting oxygen from the air into aconfined space. N₂–phobicity originates from a combinationof low nitrogen diffusion within ordered 1D pores and the unusualconfined nanospace with electron–rich Pt–N states thatenhance the electrostatic repulsion force to nitrogen. The resultingfuel cell exhibited the highest mass activity, the lowest durabilitydecline, and a record high current density of 707 mA cm^–2 at 0.8 V.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43720–43731"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090215","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":"Chiral Ti(BOX)–LMCT Catalysis Integrating Alcohol C–C Bond Cleavage with Enantioselective Radical Conjugate Addition","authors":"Hexiang Wang,&nbsp;Yunzhi Lin,&nbsp;Zhiwei Zuo","doi":"10.1021/jacs.6c16103","DOIUrl":"10.1021/jacs.6c16103","url":null,"abstract":"<p>Photochemical C–C bond cleavage can convert otherwiseinertskeletal linkages into carbon-centered radicals, but its applicationin asymmetric synthesis requires radical generation to be coordinatedwith stereocontrolled bond formation. Here we describe chiral Ti(BOX)–LMCTcatalysis that enables enantioselective radical conjugate additionthrough selective fragmentation of native alcohol C–C bonds.Alcohol coordination generates a photoactive Ti(IV)–alkoxide,whose LMCT excitation triggers β-scission to produce a carbon-centeredradical and a reduced chiral Ti species in the same photochemicalevent, with the latter implicated in the subsequent stereocontrolledbond-forming step. Structurally diverse alcohols and electron-deficientalkenes participate with high chemo- and enantioselectivity, includingsubstrates that furnish all-carbon quaternary stereocenters. Single-crystalX-ray diffraction, operando EPR, and kinetic analysis identify substrate-derivedTi(BOX)–alkoxide complexes as catalytically competent photoactivespecies. Comparative photolysis further shows that alkoxide, halide,and BOX ligands collectively influence the apparent photoreactivityof Ti–alkoxide complexes.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"42904–42912"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090220","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":"Redox Reactions in Molten Indium Halide Salts Enable the Synthesis and Shape Control of In-Pnictide Nanocrystals","authors":"Justin C. Ondry,&nbsp;Zirui Zhou,&nbsp;Luca Giordano,&nbsp;Yi-Chen Chen,&nbsp;Jun Hyuk Chang,&nbsp;Yuan Liu,&nbsp;Rebecca C. Hotton,&nbsp;Shengsong Yang,&nbsp;Zeger Hens,&nbsp;A. Paul Alivisatos,&nbsp;Dmitri V. Talapin","doi":"10.1021/jacs.6c10386","DOIUrl":"10.1021/jacs.6c10386","url":null,"abstract":"<p>Molten indium halide salts enable high-temperature andoxygen-freeprocessing and production of III–V nanocrystals, but theirredox chemistry can also induce nanocrystal decomposition. Here weshow that redox potential of indium halide melts controls the chemicalstability of InP, InAs, and InSb nanocrystals. Raman probes of halidespeciation and powder XRD of recovered solids reveal that iodide melts,such as KInI₄, can oxidize indium pnictide nanocrystals,coupling salt reduction to oxidative pnictide loss, whereas bromidemelts, such as KInBr₄, resist reduction and stabilize InPand InAs nanocrystals. This redox-tuned stability enables composition-preservingannealing that smooths (111) facets, converting round or tetrapod-likeInP and InAs particles into highly faceted tetrahedra, and promotesatomically aligned self-assembly and preferential substrate orientation.Controlled ripening in KInBr₄ yields larger III–Vcolloids inaccessible by synthesis conducted in conventional organicsolvents. Furthermore, combining molten-salt annealing with monolayerZnS growth by colloidal atomic layer deposition (c-ALD) produces significantphotoluminescence enhancement, underscoring the chemical benefitsof redox-tuned molten salt solvents for the synthesis of novel III–Vnanocrystals. Finally, we demonstrate a strategy to enhance the reactivityof reduced indium halide salts through halide coordination with astrong Lewis acid, enabling direct synthesis of InP and InAs nanocrystals.Reaction environments with highly reactive reduced indium salt engineeredin molten salts also reveal that under certain reaction conditions,unprecedented 2D InP nanoplatelets can be synthesized.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43123–43138"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101086","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":"Selective B(4)–H Alkoxylation of o-Carboranes with Alcohols via Heteroleptic Cu(I)-Photocatalyzed 1,5-HAT-Enabled Boron Radical-Polar Crossover","authors":"Li-Xin Li,&nbsp;Zi-Teng Yang,&nbsp;Shi-Chao Li,&nbsp;Chen-Rui Li,&nbsp;Pan Wang,&nbsp;Kai Hu,&nbsp;Wenjing Zhang,&nbsp;Xuenian Chen,&nbsp;Yan-Na Ma","doi":"10.1021/jacs.6c16285","DOIUrl":"https://doi.org/10.1021/jacs.6c16285","url":null,"abstract":"<p>Carboranes are an important class of boron cluster compoundswithbroad applications in medicine, materials science, and catalysis.However, the site-selective functionalization of their B–Hbonds remains a long-standing challenge owing to the nearly identicalchemical environments and high bond dissociation energies (BDEs) ofthese bonds. Traditional approaches generally rely on precious metalcatalysts, harsh reaction conditions, or substrate prefunctionalization,which significantly limit their synthetic utility. Herein, we reportthe first direct B–H/O–H cross-coupling of <em>o</em>-carboranes with alcohols, enabled by heteroleptic Cu(I) complexesunder mild photocatalytic conditions. This protocol achieves highlyregioselective B(4)–H alkoxylation with a broad substrate scopeand excellent functional group tolerance, providing a facile routeto diverse carborane-based building blocks. Mechanistic studies revealthat the benzoyl directing group effectively amplifies the differencein BDEs between B(3)–H and B(4)–H, thereby enablingselective activation of the B(4)–H bond via 1,5-hydrogen atomtransfer (HAT). Notably, for the first time, we demonstrate that aboron radical-polar crossover process mediated by the heterolepticcopper catalyst converts boron radicals into highly electrophilicboron cation intermediates, which can be directly trapped by weaklynucleophilic alcohols to form B–O bonds. This work establishesa new and general strategy for carborane B–H functionalizationvia radical pathways.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43883–43894"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173352","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":"Narrowband Emitting Tin Dion–Jacobson Perovskites through Systematic Spacer Cation Design to Suppress Metal Lone-Pair Anisotropy","authors":"Kristel M. Forlano,&nbsp;Jiahao Xie,&nbsp;Christopher T. Triggs,&nbsp;Jalianet Román-Matías,&nbsp;Daniel D. Kohler,&nbsp;Francesca Canestra,&nbsp;Cristina Femoni,&nbsp;David P. Lafayette,&nbsp;Ilia A. Guzei,&nbsp;Daniele Cortecchia,&nbsp;John C. Wright,&nbsp;Yanfa Yan,&nbsp;Song Jin","doi":"10.1021/jacs.6c11969","DOIUrl":"https://doi.org/10.1021/jacs.6c11969","url":null,"abstract":"<p>Two-dimensional (2D)Dion-Jacobson (DJ) tin perovskitesare promisinglead-free semiconductors, yet the limited number of phases reportedand their frequently broad and asymmetric photoluminescence (PL) havehindered mechanistic understanding and rational design of their optoelectronicproperties. Here, we systematically study 13 DJ Pb/Sn iodide perovskitepairs with identical diammonium spacer cations, including four newlysynthesized Sn phases, to seek structure–property trends. Weshow that narrow and symmetric PL of Pb perovskites alone does notpredict similarly favorable emission from Sn analogues. Instead, SnDJ perovskites with narrow and symmetric PL share a structural motifdefined by crystallographically equivalent perovskite pockets andminimal metal off-centering distortion, which can be achieved by symmetricspacer cations. First-principles calculations together with symbolicregression quantitatively connect this motif to reduced anisotropyof the Sn²⁺ lone pair expression and smaller excited-statestructural reorganization, consistent with suppressed vibronic broadeningof PL peaks. These structural and electronic criteria guide the identificationand synthesis of (4F-PDMA)SnI₄ (4F-PDMA = 2,3,5,6-tetrafluoro-1,4-phenylenedimethanammonium)that exhibits anticipated structural features, favorable PL characteristics,and excellent stability. This work introduces a rational spacer cationdesign strategy to suppress metal lone-pair anisotropy and achievetin DJ perovskites with narrow PL emission for future high-performanceoptoelectronic applications.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43289–43302"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173391","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":"Decoupling Electronic Coupling and Site-Energy Asymmetry in a Scaffold-Free π-Assembly","authors":"Yifei Wei,&nbsp;Jingjing Guo,&nbsp;Yuchuan Xu,&nbsp;Wei Zhang,&nbsp;Xin-Yu Tong,&nbsp;Pavlo O. Dral,&nbsp;WanZhen Liang,&nbsp;Yun-Bao Jiang,&nbsp;Dongho Kim,&nbsp;Jianbin Lin,&nbsp;Hui-Jun Zhang","doi":"10.1021/jacs.6c12873","DOIUrl":"https://doi.org/10.1021/jacs.6c12873","url":null,"abstract":"<p>Inconventional π-stacked systems, electronic coupling (<em>J</em>) and site-energy asymmetry (<em>Δε</em>) are governed by the same structural coordinate. Co-facial packingmaximizes <em>J</em> but enforces <em>Δε</em> ≈ 0, yielding symmetry-equivalent local-excitation-charge-transfer(LE-CT) manifolds near the charge-resonance/excimer limit, whereaschemically differentiated donor–acceptor systems impose <em>Δε</em> ≫ <em>J</em> and favor localizedCT states. The intermediate regime, with finite static <em>Δε</em> while preserving strong coupling, thus remains difficult to access.Nature achieves this in photosynthetic special pairs by separatingthe structural origins of <em>J</em> (cofactor stacking) and <em>Δε</em> (protein electrostatics). Inspired by thisprinciple, we construct a scaffold-free hierarchical π-assemblyof four <em>C</em>₃-symmetric perylene diimidetriads, which comprises strongly coupled dimeric cores and monomer-likeperipheral units. Directional C–H···O═Chydrogen bonding renders the core chromophores electronically inequivalent,producing static <em>Δε</em>_LE (∼12meV) within a pair whose excitonic coupling, determined experimentallyfrom a Spano vibronic analysis, is 93 meV. Electronic-structure calculationspredict that this asymmetry is embedded in the lowest excited-statemanifold at the Franck–Condon geometry, where the modest ground-stateasymmetry yields a much larger <em>Δε</em>_CT (∼210 meV) splitting of opposing CT configurations.Femtosecond transient absorption resolves a 1.2 ps evolution towardincreased ionic spectral character, while nanosecond spectroscopyand photoluminescence show persistence over ∼20 ns as a radiativelyactive excited-state ensemble. These results establish hierarchicalself-assembly as a strategy for decoupling electronic coupling fromsite-energy asymmetry and provide a structural basis for a directionallybiased LE-CT manifold predicted by electronic-structure calculationsand consistent with the observed excited-state dynamics.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43389–43400"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173467","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":"Site-Selective Electronic Structure and Dynamical Softness in the Metallic Antiferromagnet Mn3CuN","authors":"Aryan Keshri,&nbsp;Sourav Chowdhury,&nbsp;Naveen Goyal,&nbsp;Anju Ahlawat,&nbsp;Pushpendra Gupta,&nbsp;Garima Kaura,&nbsp;Ram Janay Choudhury,&nbsp;Moritz Hoesch,&nbsp;N. Ravishankar,&nbsp;Manuel Bibes,&nbsp;A. C. Garcia-Castro,&nbsp;Sujit Das","doi":"10.1021/jacs.6c16429","DOIUrl":"https://doi.org/10.1021/jacs.6c16429","url":null,"abstract":"<p>Electronic structure, local bonding,and magnetic order are intimatelycoupled in correlated antiperovskites, making it challenging to distinguishthe contributions of individual crystallographic sites to their collectiveproperties. Here, we combine element-specific X-ray spectroscopy,temperature-dependent X-ray absorption spectroscopy, X-ray magneticcircular dichroism, electrical transport measurements, and first-principlescalculations to investigate the site-selective electronic structureof epitaxial metallic antiferromagnetic Mn₃CuN thin films.We reveal an anomalous charge distribution characterized by effectivelow-valent Mn and subvalent Cu states stabilized by covalent Mn–N–Cuinteractions. While the Mn sublattice forms a robust noncollinearantiferromagnetic framework below ∼120 K, the electronicallydistinct Cu sites remain magnetically inactive yet exhibit pronouncedtemperature-dependent local structural evolution. Despite the onsetof magnetic ordering, Mn₃CuN retains metallic transportwith a near-zero temperature coefficient of resistivity (NZ-TCR),indicating minimal coupling between magnetic ordering and charge transport.These findings demonstrate that site-selective electronic structureenables chemically differentiated lattice dynamics while preservinga robust magnetic framework, establishing Mn₃CuN antiperovskitein which electronic, structural, and magnetic responses can be selectivelydecoupled. This work provides a materials design principle for engineeringmultifunctional metallic antiperovskites through site-selective electronicstructure and local chemical bonding.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43854–43863"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173468","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":"De Novo Discovery of Cysteine-Targeted Reversible Covalent Cyclic Peptides with Prolonged Residence Time via Phage Display","authors":"Yuqian Zhang,&nbsp;Mengzhu Qi,&nbsp;Xiankai Liu,&nbsp;Yukun Zhou,&nbsp;Yanmei Wang,&nbsp;Xing Xiao,&nbsp;Yapei Wu,&nbsp;Wei Gao,&nbsp;Yang Liu,&nbsp;Yiwu Zheng","doi":"10.1021/jacs.6c17599","DOIUrl":"https://doi.org/10.1021/jacs.6c17599","url":null,"abstract":"<p>Reversible covalent targeting of cysteine residues offersa powerfulstrategy for generating potent and tunable ligands, but designingelectrophiles with balanced reactivity, stability, and reversiblebinding remains challenging. Here, we systematically optimized reversibleα,β-unsaturated nitrile electrophiles and incorporatedthe selected warhead with prolonged residence time into phage-displayedpeptides to construct a library of reversible covalent cyclic peptides.Screening this library against Keap1 enabled the de novo identificationof ligands with nanomolar affinities, demonstrating a 5–100-foldimprovement in binding potency relative to the corresponding noncovalentcyclic peptides. The most potent ligand, cyclic peptide <strong>32</strong>, exhibits a <em>K</em>_i of 3.7 nM, retains bindingunder thiol-rich conditions, and can capture Keap1 from a complexcellular environment. Mechanistic analysis reveals that peptide-mediatedtargeting in cyclic peptide <strong>32</strong> positions the reversiblecovalent warhead to react rapidly with Keap1 Cys434 while maintainingprolonged residence, allowing covalent bond formation to keep pacewith the transient binding dynamics of the peptide–proteininteraction. Overall, this work establishes a general strategy forintegrating tunable reversible covalent chemistry into geneticallyencoded peptide libraries, enabling de novo discovery of high-affinityligands.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43925–43936"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173594","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":"Calorimetric and Quasielastic Neutron Scattering Studies on a Mg-Ion Conductor Using a Metal–Organic Framework MIL-101 Involving Acetonitrile","authors":"Shun Sato,&nbsp;Hiroshi Akiba,&nbsp;Yoshinori Ohmasa,&nbsp;Takeshi Yamada,&nbsp;Kaori Taniguchi,&nbsp;Masaaki Sadakiyo,&nbsp;Iwao Matsuda,&nbsp;Genki Kobayashi,&nbsp;Osamu Yamamuro","doi":"10.1021/jacs.6c11926","DOIUrl":"https://doi.org/10.1021/jacs.6c11926","url":null,"abstract":"<p>A metal–organic framework(MOF) MIL-101 containing Mg(TFSI)₂ (TFSI: bis(trifluoromethanesulfonyl)imide)and guest moleculeswithin pores exhibits high Mg²⁺ conductivity (&gt;10^–3 S cm^–1) at room temperature andis attractingattention as a hopeful solid Mg conductor. To investigate the phasebehavior and the dynamics of acetonitrile (AN) molecules in the pores,heat capacity (<em>C</em>_<em>p</em>) andquasielastic neutron scattering (QENS) experiments were performedfor MIL-101/Mg(TFSI)₂/AN, MIL-101/AN, bulk AN/Mg(TFSI)₂, bulk AN, and dry MIL-101. The <em>C</em>_<em>p</em> measurement of MIL-101/AN revealed a broad phasetransition around 110–250 K, corresponding to some sort oforder/disorder process of AN molecules within the pores. A similar <em>C</em>_<em>p</em> peak accompanied by a glasstransition at the <em>C</em>_<em>p</em> risingpart appeared in MIL-101/Mg(TFSI)₂/AN. This glass transitioncorresponds to the freezing of the AN motion in the pores. The samplescontaining AN exhibited QENS broadening above the phase transitions.The QENS spectra of the samples with Mg(TFSI)₂ were wellexplained by the jump diffusion model, while those without Mg(TFSI)₂ by the continuous diffusion model. The jump length was about1.6 Å, which is thought to be related to the connection/disconnectionprocesses of AN molecules to Mg²⁺ ions. The diffusion coefficientof AN molecules decreased in the order of bulk AN &gt; bulk AN/Mg(TFSI)₂ &gt; MIL-101/AN &gt; MIL-101/Mg(TFSI)₂/AN. OnlyMIL-101/Mg(TFSI)₂/AN exhibited non-Arrhenius temperaturedependence. Theseresults are consistent with our proposed model that the coordinationof AN to Mg²⁺ shields interionic electrostatic interactionsand enhances the Mg²⁺ mobility, leading to the high Mg²⁺ conductivity in MIL-101/Mg(TFSI)₂/AN.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 40","pages":"43303–43312"},"PeriodicalIF":16.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173696","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}