Chemistry of Materials最新文献

{"title":"Unprecedented\u0000Pd(II) Metal–Organic Cages for\u0000Simultaneous Adsorption of Iodine Species","authors":"Risikeshan Pradhan,Raghunath Singha,Pijush De,Monotosh Dalapati,Pankaj Maity,Debashree Manna,Dipak Samanta","doi":"10.1021/acs.chemmater.6c01650","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01650","url":null,"abstract":"Abstract Metal–organic cages (MOCs) with unconventional topologies remain rare owing to the challenges associated with controlling coordination-driven self-assembly. Herein, we report the self-assembly of two unique Pd(II)-based coordination cages–peanut-shaped cage (C1, M18L14) and hemicage (C2, M12M2L22), from semiflexible tetratopic pyridyl ligands incorporating 9,10-dihydroanthracene and benzene backbones, respectively. Single-crystal X-ray diffraction studies reveal that cage C1 adopts a rare peanut-shaped structure comprising two interconnected cavities and both inward- and outward-oriented Pd(II) nodes, generating a highly electron-rich confined environment. In contrast, C2 forms an unprecedented boat-shaped architecture assembled through the cooperative incorporation of 90° and 180° Pd(II) acceptors within a single discrete cage. Despite their amorphous and nonporous nature, these assemblies demonstrate exceptional dual-capture performance toward volatile iodine species. Notably, C1 achieves iodine uptake capacities of 2.62 g g–1 under static vapor-phase conditions and 1.21 g g–1 under dynamic flow conditions, together with efficient CH3I adsorption of up to 1.05 g g–1 at 75 °C. Spectroscopic investigations and theoretical calculations reveal that the adsorption process is driven by synergistic charge-transfer interactions, polyiodide formation, electrostatic stabilization, and cavity confinement. Furthermore, both cages display excellent retention capability and recyclability, highlighting their potential as robust materials for radioactive iodine sequestration and environmental remediation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"40 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anion and Cation (Co-)intercalation Behavior from an Inorganic Molten Salt for Dual-Ion Batteries","authors":"Hrishikesh S. Srinivasan,&nbsp;Seunga Heo,&nbsp;Emily S. Doyle,&nbsp;Chibueze V. Amanchukwu","doi":"10.1021/acs.chemmater.6c01280","DOIUrl":"10.1021/acs.chemmater.6c01280","url":null,"abstract":"<p>Long-duration energystorage is needed to acceleratedecarbonization.Lithium-ion batteries are currently state-of-the-art but require costlytransition metal oxide cathodes, which can limit their scalability.Dual-graphite batteries are a promising chemistry featuring a graphiteanode and graphite cathode, where cation and anion intercalation occurat the former and latter electrodes, respectively. Conventional small-molecule-basedelectrolytes face safety issues due to their flammability and volatility,and they limit the energy density of dual-graphite batteries due tothe presence of species other than the active ions. Molten salt electrolytesare thus a promising alternative to conventional dual-graphite batteryelectrolytes due to their intrinsic safety and energy density. Here,we report the investigation of a low-melting, single-cation imide-basedbinary molten salt electrolyte to enable “Carbon-and-Salt”batteries. We find that both anions in the Li(FSI)_<em>x</em>(FTFSI)_{1–<em>x</em>} electrolytesthat were studied reversibly intercalate into graphite cathodes, butthat FTFSI^– preferentially intercalates and is presentin greater compositions in anion-graphite intercalation compoundscompared to the bulk electrolytes. Furthermore, we find that lithiumco-intercalates with the anions, suggesting the inability of anionsto fully de-solvate from tightly-bound aggregate networks. The systematicinvestigation of anion and cation (co-)intercalation behavior fromimide-based molten salts is important to guide the design of next-generationsolvent-free and transition-metal-free “Carbon-and-Salt”batteries.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9902–9915"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tunable Magnetotransport across Competing Magnetic Phases in the Distorted Kagome Antiferromagnet HoPtSn","authors":"Abhinav Agarwal,&nbsp;Snehashish Chatterjee,&nbsp;Andrzej Ptok,&nbsp;Orest Pavlosiuk,&nbsp;Piotr Wiśniewski,&nbsp;Dariusz Kaczorowski","doi":"10.1021/acs.chemmater.6c00030","DOIUrl":"10.1021/acs.chemmater.6c00030","url":null,"abstract":"<p>Competing magneticphases in frustrated systems provide a fertileground for unusual magnetic and electronic responses owing to theirsensitivity to external perturbations. The distorted kagome antiferromagnetHoPtSn is an example of such a system, exhibiting successive magnetictransitions and multiple field-induced metamagnetic states at lowtemperatures. Here, we combine magnetic susceptibility, heat capacity,magnetotransport, and magnetization under hydrostatic pressure measurementson single crystals to investigate the interplay between the competingmagnetic phases in HoPtSn. At ambient pressure, HoPtSn undergoes twomagnetic transitions at <em>T</em>_N1 ≈ 7.3K and <em>T</em>_N2 ≈ 2.7 K. The lower-temperaturetransition is accompanied by pronounced thermal and magnetic hysteresis,indicating its first-order character. Magnetization measurements reveala series of field-induced transitions and a strongly anisotropic low-temperaturephase diagram. Correspondingly, the magnetotransport exhibits sharpanomalies across the metamagnetic transitions together with clearfield-history dependence, while Hall resistivity measurements revealadditional features that emerge within the ordered state. These resultspoint to a strong coupling between electronic transport and magneticreconstruction. Hydrostatic pressure leaves <em>T</em>_N1 nearly unchanged, while it gradually shifts <em>T</em>_N2 to higher temperatures, indicating that the competingmagnetic phases respond differently to lattice compression, whilethe first-order transition remains robust throughout the investigatedpressure range. Electronic structure calculations reveal several Dirac-likecrossings near the Fermi level, suggesting possible interplay betweenthese features and the complex magnetic phase space. Taken together,our results show that HoPtSn hosts a delicate balance between competingmagnetic states, whose reconstruction leaves distinct signatures inthe transport properties and can be continuously tuned by pressure.These findings highlight distorted kagome antiferromagnets as a promisingplatform for exploring the interplay between magnetic phase competitionand electronic transport.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9754–9762"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-Temperature Combustion Synthesis of Metals and Metal Oxides via Isobutylene-Generating Complexing Agents","authors":"Thomas W. Colburn,&nbsp;Abigail Carbone,&nbsp;David W. Collinson,&nbsp;Robert D. Miller,&nbsp;Reinhold H. Dauskardt","doi":"10.1021/acs.chemmater.6c01946","DOIUrl":"10.1021/acs.chemmater.6c01946","url":null,"abstract":"<p>Solution combustion synthesis (SCS) is a low-temperaturesynthesistechnique leveraging a highly exothermic combustion reaction betweena metal complexed by an organic fuel and oxidant (e.g., nitrate) togenerate metals and metal compounds such as oxides, nitrides, andcarbides at reduced applied temperatures compared to conventionalsolution methods. However, many ideal hydrocarbon fuels for low-temperaturecombustion processes are too volatile and noncoordinating to metalcations in solution, making them poorly suited for SCS. Here, we presentSCS complexing agents, which contain <em>t</em>-butyl esterfunctionality capable of generating isobutylene in situ at low appliedtemperatures, which acts as a potent fuel in the combustion process.We form four important oxides and metal/oxide combined nanostructures:InO_x, MnO_x, NiO_x, and CoO_x at applied temperatures &lt;150 °C including the formationof InOx at &lt;80 °C which is, to our knowledge, the lowest purelyheat-initiated SCS reaction observed to date. This work reveals thatisobutylene-generating fuels, particularly for the indium cation,are a powerful tool for applications demanding oxides at low formationtemperatures.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10242–10250"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microwave-Assisted Facile Synthesis and Microenvironment Engineering of Enaminone COFs for Efficient Photocatalytic H2O2 Production","authors":"Sagarmani Rasaily,&nbsp;Nayan Sarkar,&nbsp;Sukalyan Chatterjee,&nbsp;Saurabh Vinod Parmar,&nbsp;Sudip Maity,&nbsp;Dipanjan Majumder,&nbsp;Anirban Roy,&nbsp;Vidya Avasare,&nbsp;Sujit K. Ghosh","doi":"10.1021/acs.chemmater.6c01601","DOIUrl":"10.1021/acs.chemmater.6c01601","url":null,"abstract":"<p>Covalent organic frameworks (COFs) have emerged as promisingmetal-freephotocatalysts; however, their widespread application is often hinderedby the time-consuming solvothermal preparation. Developing rapid andcost-effective routes to highly crystalline COFs is therefore essentialfor expanding their practical utility. In this regard, microwave-assistedsynthesis offers a distinct advantage over conventional solvothermalmethods by shortening reaction times from days to minutes while simultaneouslyimproving crystallinity. Here, we report a microwave-assisted strategyfor synthesizing enaminone-COFs via the Michael addition-eliminationreaction, achieving &gt;90% yields within 60 min. The developed microwave-assistedstrategy demonstrated broad versatility by enabling the synthesisof six distinct enaminone COFs. Notably, the microwave-synthesizedCOFs exhibited physical properties similar to previously reportedframeworks. Among the synthesized enaminone COFs, COF-Tz-MW and COF-Bz-MWwere rationally engineered with tunable nitrogen content, creatingdistinct local microenvironments that modulate the acceptor–donor–acceptor(A–D–A) charge-transfer pathway for efficient photocatalyticH₂O₂ synthesis. This molecular-level variationwas systematically investigated to elucidate its influence on chargedistribution and photophysical properties, revealing a clear structure–reactivitycorrelation of enaminone-COFs in H₂O₂ photosynthesis.Notably, the COF-Bz-MW demonstrated effective charge separation andsuperior H₂O₂ production performance with aproduction rate of 8.70 mmol g^–1 h^–1 from blue LED-H₂O–O₂. Theoretical studiesrevealed that the enaminone moiety coupled with the benzene core aminecreates an optimized A–D–A configuration, enhancingO₂-adsorption and promoting efficient photocatalytic H₂O₂ production. Our work pioneers a paradigm forfacile and rapid synthesis of enaminone COFs, while demonstratingN-site microenvironment engineering as an effective strategy to advanceCOF-based photocatalysts for efficient photocatalytic H₂O₂ production.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10062–10074"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Response of Metal Electrodes in Contemporary Batteries","authors":"Kaan Kizmaz,&nbsp;Jelena Popovic-Neuber","doi":"10.1021/acs.chemmater.6c01486","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01486","url":null,"abstract":"<p>Alkali metal electrodesare considered promising enablersof next-generationhigh energy density batteries and are commonly utilized in half cellsfor electrochemical characterization of battery materials. Their highreactivity with common battery electrolytes and nonplanar electrodepositionunder constant current drives complex interphase formation and morphologicalinstability, challenging a stable and reliable application. This reviewhighlights how electrochemical methods─specifically electrochemicalimpedance spectroscopy (EIS) and galvanostatic polarization in symmetriccells─provide powerful, in situ, and nondestructive tools tostudy material properties and the kinetics of their degradation incells. We summarize recent key findings and demonstrate how time,temperature, and current-dependent electrochemical responses yieldvaluable insights into the electrochemical and morphological stabilityand kinetics of both naturally formed and artificial alkali metalinterphases. We further show how both methods are effectively usedto understand the charge-transfer process and diffusion under anion-blockingconditions and determine effective cationic transference numbers ofa variety of contemporary battery electrolytes, essential for theirstructure–property evaluation.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9641–9658"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupling Photonic Bandgap Engineering with Photochromism for Upconversion Luminescence Modulation","authors":"Yuhuan Li,&nbsp;Anjun Huang,&nbsp;Xinhao Cai,&nbsp;Heping Zhao,&nbsp;Yingzhu Zi,&nbsp;Xue Bai,&nbsp;Yue Liu,&nbsp;Yangke Cun,&nbsp;Zhiguo Song,&nbsp;Jianbei Qiu,&nbsp;Peng Ren,&nbsp;Zhengwen Yang","doi":"10.1021/acs.chemmater.6c02176","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02176","url":null,"abstract":"<p>Reversible and wavelength-selective luminescence modulationisessential for advanced optical encryption, anticounterfeiting, andadaptive photonic devices. However, conventional photochromism-inducedluminescence regulation is usually governed by a reabsorption effect,leading to nonselective intensity modulation. Herein, PbWO₄:Yb³⁺/Er³⁺ inverse opal photonic crystals werefabricated through a template-assisted stepwise infiltration strategy,in which W- and Pb-containing precursor sols were sequentially introducedto avoid precipitation and ensure the formation of ordered photonicarchitectures. The obtained PbWO₄:Yb³⁺/Er³⁺ inverse opals exhibit tunable photonic stop-bands and distinctstructural colors. By matching the photonic bandgap with Er³⁺ emission bands, wavelength-selective inhibition and band-edge-enhancedupconversion luminescence were achieved, enabling the regulation ofthe red-to-green emission ratio. X-ray-induced photochromism originatesfrom the synergistic effect of oxygen vacancy-related color centerformation and polaron hopping associated with W⁶⁺/W⁵⁺ mixed-valence states, providing a reversible route for overallemission intensity modulation. Benefiting from the structural-colormasking effect and coloration-induced upconversion luminescence modulation,concealed information writing and 980 nm laser-readable optical patternswere demonstrated. This work provides an effective strategy for integratingphotonic bandgap engineering with photochromism toward upconversionluminescence modulation and advanced optical anticounterfeiting applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10366–10374"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-Temperature Synthesis of Large-Area Hexagonal Boron Nitride Films on Diverse Substrates by Plasma Afterglow Deposition","authors":"Souvik Bhattacharya,&nbsp;He Lin Zhao,&nbsp;Amelia Schaeffer,&nbsp;Zachary Martin,&nbsp;Matthew P. Confer,&nbsp;Adam Rousseau,&nbsp;Ranveer Singh,&nbsp;Zhiting Tian,&nbsp;Pinshane Y. Huang,&nbsp;Arend M. van der Zande,&nbsp;R. Mohan Sankaran","doi":"10.1021/acs.chemmater.6c01663","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01663","url":null,"abstract":"<p>Hexagonal boron nitride(hBN) is a van der Waals materialwithexcellent insulating properties that make it well-suited as a gatedielectric in 2D electronic devices. In recent years, the discoveryof an ever-increasing list of properties has led to a much broaderrange of potential applications, including quantum photonics, memristivedevices, and extreme-environment coatings. However, current growthmethods for hBN films are characterized by a narrow selection of substratesand high temperatures that require transfer and limit scale-up. Here,we report a remote plasma-activated approach to directly synthesizelarge-area hBN films on a diverse range of representative metallic,semiconducting, and amorphous insulating substrates. Specifically,we employ the spatial afterglow of an Ar/H₂ plasma to activateammonia borane, which enables the growth of thick (&gt;30 nm), uniform,and stoichiometric films on substrates such as Si, SiO₂, glass, fused silica, Mo, and Al. Systematic spectroscopic characterizationreveals that hBN films can be grown as low as 300 °C. Furthermore,plasma afterglow-grown hBN films exhibit mechanical, electrical, andthermal properties on par with or exceeding those reported by alternatesynthesis methods. These results establish plasma afterglow growthfor the direct integration of hBN into a wide range of emerging technologies.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10095–10105"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning Interatomic Potentials for Modeling Solid-State Batteries","authors":"Mgcini Keith Phuthi,&nbsp;Grace Wei,&nbsp;Bryant Li,&nbsp;Sauradeep Majumdar,&nbsp;Venkata Surya Chaitanya Kolluru,&nbsp;Nitesh Kumar,&nbsp;Samuel Blau,&nbsp;Pieremanuele Canepa,&nbsp;Maria K. Y. Chan,&nbsp;Rafael Gomez-Bombarelli,&nbsp;Kristin Persson,&nbsp;Gerbrand Ceder,&nbsp;Shyue Ping Ong","doi":"10.1021/acs.chemmater.6c01051","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01051","url":null,"abstract":"<p>Atomistic simulations can provide critical insights intothe fundamentalbehavior of battery materials. A necessary input for such simulationsis a description of the potential energy surface (PES). Over the pastdecade, machine learning interatomic potentials (MLIPs) have emergedas a powerful approach to model the PES at near-first-principles accuracywith orders of magnitude lower computational cost. In this perspective,we examine the role of atomistic simulation in battery research, especiallyin the context of the capabilities afforded by MLIPs. We outline theiradvantages and trade-offs relative to <em>ab initio</em> methods and discuss how they enable the prediction of key intrinsicproperties relevant to battery materials, especially for solid statebatteries. We further explore their potential for modeling interfacesand chemical reactivity, as well as their integration into high-throughputscreening and materials discovery workflows. Finally, we highlightpromising applications and identify requirements for the next generationof MLIPs to advance the study of battery materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9623–9640"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activating\u0000Interstitial Oxygen Conduction in Sr3V2O8 Palmierite Oxides Through Minimal\u0000Mo-Substitution","authors":"Abdulkadir Olatunbosun Biffo,Anastasia K. Lavrinenko,Hailin Ma,Shengnan Zhang,Till Frümling,Alexandros Vasileiadis,Theodosios Famprikis,Pedro B. Groszewicz","doi":"10.1021/acs.chemmater.6c01807","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01807","url":null,"abstract":"Abstract The palmierite oxides are a promising family of ion conductors, and understanding how compositional modification affects their structure and, in turn, their ionic conductivity is pivotal for unlocking high ionic conductivity in these solid electrolytes. Here, we investigate the Sr3V2-xMoxO8+x/2 series (0 ≤ x ≤ 0.4), establishing a solubility limit at x = 0.2, and demonstrating that Mo-substituted compositions exhibit bulk O2– conductivity approximately 2 orders of magnitude higher than the pristine composition at 600 °C. Combined X-ray and neutron diffraction refinement shows little change in the average crystallographic structure, prompting questions about its local structure and dynamics. Using ab initio molecular dynamics, bond-valence site-energy calculations, and 51V and 17O solid-state nuclear magnetic resonance spectroscopy supported by density functional theory calculations, we demonstrate that Mo6+ incorporation generates a new oxygen environment consistent with the formation of a charge-compensating interstitial O3 site. While V5+ remains tetrahedrally coordinated throughout the series, Mo6+ exhibits both MoO4 and distorted trigonal bipyramidal MoO5 coordination polyhedra, with the latter arising from the occupation of O3. This O3 site is proposed to bridge neighboring MOn polyhedra along the ab-plane, shortening the O2– jump distances and shifting the conduction mechanism from a 3D cooperative rotational mechanism to a 2D interstitial-based one.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"412 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}