Chemistry of Materials最新文献

{"title":"Suppressing Second-Order Jahn–Teller Distortion of Bi3+ by Smaller Y3+-Substitution in Bi3O4Cl","authors":"Kosei Takano,&nbsp;Kanta Ogawa,&nbsp;Takafumi Yamamoto","doi":"10.1021/acs.chemmater.6c01862","DOIUrl":"10.1021/acs.chemmater.6c01862","url":null,"abstract":"<p>Controllinglocal coordination environments of second-orderJahn–Teller(SOJT)-active post-transition metal cations remains a significantchallenge due to their inherent preference for asymmetric environments.Previously, we reported that the high-symmetry Y³⁺ sitein layered Bi₂YO₄Cl can serve as a structuraltemplate to stabilize a centrosymmetric coordination environment forBi³⁺ (up to 40% replacement), effectively suppressing theSOJT distortion. In this study, we re-examined the synthesis processof Bi₂(Y_{1–<em>x</em>}Bi_<em>x</em>)O₄Cl and successfully increased the Bioccupancy at the high-symmetry site to <em>x</em> = 0.8, approximatelydoubling the previously accessible composition range. At this highsubstitution level, the system is practically better described asa Y-substituted Bi₃O₄Cl rather than a Bi-substitutedBi₂YO₄Cl. First-principles calculations, togetherwith comparative experiments using other trivalent cation dopantsof different ionic radii, reveal that chemical pressure is a key factorgoverning the suppression of the SOJT distortion and the resultingband gap narrowing. These findings provide insight into the stabilizationof unusually high-symmetry coordination environments in SOJT-activepost-transition-metal compounds for tuning their electronic structures.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10174–10184"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010260","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":"COFFlow: Building-Block-Based Generative Modeling for Two-Dimensional Covalent Organic Framework Discovery","authors":"Yuanhui Pan,&nbsp;Yunrui Yan,&nbsp;Cheng Zeng,&nbsp;Jirui Jin,&nbsp;Mingjie Liu","doi":"10.1021/acs.chemmater.6c01524","DOIUrl":"10.1021/acs.chemmater.6c01524","url":null,"abstract":"<p>Two-dimensional covalent organic frameworks (2D COFs)are promisingporous materials with vast yet largely unexplored design space arisingfrom diverse building blocks (BBs) and crystal topologies. Efficientcrystal structure prediction (CSP) and inverse design of 2D COFs thereforeremain highly challenging. Here, we develop <em>COFFlow</em>, a flow-matching-based generative framework for CSP of 2D COFs.A COF-specific deconstruction algorithm is introduced to consistentlydecompose periodic COFs into experimentally relevant BBs across diversetopologies, enabling direct generative assembly of periodic frameworksfrom BB representations. Systematic evaluations demonstrate that <em>COFFlow</em> can reliably and efficiently generate structurallyconsistent and chemically valid 2D COFs. Beyond the commonly usedmatch rate (MR), we further introduce validity rate (VR) to assessthe chemical validity of generated structures. The models exhibitnontrivial extrapolation capability toward unseen BBs and crystaltopologies, although preserving chemical validity under strong distributionshifts remains challenging. To demonstrate the practical utility ofthe framework, we integrated <em>COFFlow</em> with data-drivenscreening and inverse design of 2D COFs for methane storage. Usingdeliverable capacity as the target metric for adsorbed natural gasapplication, we identified several previously unreported 2D COFs withperformance among the highest reported to date. More broadly, thiswork establishes a scalable framework for AI-driven discovery anddesign of reticular materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10036–10049"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049480","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":"Nucleation and Coalescence of Wüstite-like Motifs in Oxygen-Deficient Magnetite: A Deep-Potential Molecular Dynamics Study","authors":"Zeng Liang,&nbsp;Kejiang Li,&nbsp;Jianliang Zhang,&nbsp;Alberto N. Conejo","doi":"10.1021/acs.chemmater.6c02276","DOIUrl":"10.1021/acs.chemmater.6c02276","url":null,"abstract":"<p>Oxygen loss in magnetite drives thecation redistributionand localstructural reconstruction that control the rate of iron oxide reduction,but this coupling has resisted direct simulation: the reconstructiondevelops far beyond DFT-accessible scales, and classical potentialscannot describe mixed-valence Fe–O with the required fidelity.We developed a DFT-validated Fe–O Deep Potential trained onbulk, defective, and surface configurations and applied it in large-scalemolecular dynamics with an imposed stochastic oxygen-removal protocol.The potential reproduces DFT energy and force trends together withvacancy and surface energetics. DFT single-point checks on oxygen-deficientconfigurations and equation-of-state calculations for Fe₃O₄ and FeO further delineate the transferability of thepotential, with larger deviations emerging in the most strongly oxygen-deficientstates. As oxygen is removed, four-coordinated O environments decreasewhile six-coordinated wüstite-like motifs emerge, grow, andcoalesce into extended local domains. Deep-Potential nudged elasticband (DP-NEB) calculations, benchmarked against selected DFT single-pointenergies, show that the coupled O/Fe-vacancy configuration gives thelowest Fe-migration barrier among the selected local rearrangementpathways. Time-windowed mean-squared displacements yield apparentFe and O diffusivities that evolve in the nonstationary lattice. Thesesimulations establish a defect-mediated solid-state response towardwüstite-like local order under imposed oxygen-deficient conditions,rather than the formation of a complete equilibrium Fe_1–xO phase. The protocol isolates oxide-side reconstruction and doesnot explicitly treat hydrogen chemistry.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10375–10387"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090879","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":"A Combinatorial Approach to the Design of Boronate Ester Hydrogels Reveals the Remarkable Binding Properties of a Bicyclic Diol","authors":"Léa Terriac,&nbsp;Khaled Alsabil,&nbsp;Garance Saint-Pé,&nbsp;Guillaume Viault,&nbsp;Yves Maugars,&nbsp;Catherine Garnier,&nbsp;Jean-Jacques Helesbeux,&nbsp;Vianney Delplace","doi":"10.1021/acs.chemmater.6c01255","DOIUrl":"10.1021/acs.chemmater.6c01255","url":null,"abstract":"<p>Viscoelastic hydrogels are increasingly being used inthe biomedicalfield, with applications ranging from 3D cell culture to drug delivery.Boronate ester (BE) formation is one of the dynamic covalent reactionsthat can be used for viscoelastic hydrogel design. BE formation standsout for the stability and relative bioorthogonality of its precursors,i.e., phenylboronic acids and diols. However, BE hydrogels usuallylack stability, are soft, and behave like fast-relaxing viscoelasticliquids at physiological pH due to low BE binding strength. To addressthese limitations, we performed a combinatorial screening of BE crosslinkingpairs based on PBAs and cyclic <em>cis</em>-diols, using hyaluronicacid as a base polymer. Our study revealed the unique ability of norbodiol,a bridged bicyclic <em>cis</em>-diol, to form BE hydrogelswith all the PBAs tested. We demonstrated that this is due to norbodiol’sexceptional association constants (<em>K</em>_a)with PBAs, which can reach values of up to 6600 M^–1. Compared to a list of other diols, we further showed that the remarkableproperties of norbodiol could be explained by its rigid bicyclic structureand the specific three-dimensional orientation of its two hydroxylgroups. These findings provide initial insights toward a deeper understandingof the optimal diol structure for BE formation and stability. Norbodiol-basedBE crosslinking produced hydrogels whose relaxation properties were20- to 200-fold greater than those of previous systems. We furtheroptimized two hydrogel formulations with single or dual BE crosslinkingfor use in various biomedical applications, highlighting the potentialof our discovery.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9886–9901"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973832","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":"Phase Selectivity in Borate Flux Synthesis Using Refractory Additives","authors":"Gregory Bassen,&nbsp;Allana G. Iwanicki,&nbsp;Maxime A. Siegler,&nbsp;Sarah Okandey,&nbsp;Elaine Flowers,&nbsp;Rebecca Han,&nbsp;Sydney Reiser,&nbsp;Brandon Wilfong,&nbsp;Davor Tolj,&nbsp;Tyrel M. McQueen","doi":"10.1021/acs.chemmater.6c01919","DOIUrl":"10.1021/acs.chemmater.6c01919","url":null,"abstract":"<p>Here, we report a novel approach to borate flux synthesisin whichrefractory oxide additives alter reaction phase outcome. In the absenceof refractory additives, reactions of copper oxide and boron oxideflux yielded single crystals of the previously reported Cu₁₅(BO₃)₆(B₂O₅)₂O₂ (Cu₃B₂O₆), containingsolely trigonal planar-coordinated borate monomers and dimers. Additionof TiO₂ led to the discovery of a novel structural prototypeCu_{7–<em>x</em>+<em>y</em>}Ti_<em>x</em>(BO₃)(B₂O₅)(B₃O₇)O (Cu_{7–<em>x</em>+<em>y</em>}Ti_<em>x</em>B₆O₁₆), which crystallizes in space group <em>P</em>1̅, with <em>a</em> = 3.31989(4) Å, <em>b</em> = 10.54906(13) Å, <em>c</em> = 17.9143(2) Å, α= 75.5076(10)°, β = 88.8619(10)°, and γ = 86.7381(10)°for <em>x</em> = 0.276(7), <em>y</em> = 0.0135(15).It consists of quasi-2D layers of Cu²⁺ cations enclosingtrigonal planar borate monomers, dimers, and the uncommon (B₃O₇)^5– trimer. Adjacent layers are connectedby oxygen and disordered Cu/Ti sites. In contrast, both ZrO₂ and HfO₂ grew single crystals of the previously reportedmaterial CuB₂O₄ containing solely tetrahedrallycoordinated boron in a 3D framework. Ex situ X-ray μCT imagingof the ZrO₂ reaction shows CuB₂O₄ crystals growing at the interface of ZrO₂ and the flux,suggesting that ZrO₂ (and by extension, HfO₂) acts as a heterogeneous nucleation substrate that stabilizes thefour-coordinate boron tetrahedra. Magnetization of Cu_{7–<em>x</em>+<em>y</em>}Ti_<em>x</em>B₆O₁₆ is reported, showing an antiferromagnetictransition at <em>T</em>_<em>N</em> = 12.8K. We then differentiate refractory additives into two distinct classes,flux-resistant and flux-susceptible, with ZrO₂ and HfO₂ as B₂O₃-flux-resistant refractory additivesand TiO₂ as a B₂O₃-flux-susceptiblerefractory additive. These results demonstrate that refractory additivescan provide a useful handle for directing phase formation and accessingnew materials in flux synthesis, and provide challenge cases to benchmarkemerging AI models in unconventional materials stabilization and crystalgrowth methods.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10231–10241"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148984950","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":"A Macroscopic Polarizable Piezocatalyst of Bismuth Selenite Fluoride Derived from BiOIO3 with Highly Efficient Hydrogen Evolution","authors":"Tianhui Wu,&nbsp;Wenwen Kong,&nbsp;Miao Zhang,&nbsp;Ziyang Wang,&nbsp;Shizheng Li,&nbsp;Weiwei Cao,&nbsp;Jianmin Gu,&nbsp;Desong Wang","doi":"10.1021/acs.chemmater.6c01126","DOIUrl":"10.1021/acs.chemmater.6c01126","url":null,"abstract":"<p>Piezocatalytic water splitting presents an emerging routefor producing“green hydrogen” that can overcome several limitationsof photocatalytic and electrocatalytic systems. However, existingpiezocatalysts are few, and the insufficient polarization efficiencyof these piezocatalysts is a critical obstacle to practical applications.Rational design of a macroscopic polarizable piezocatalyst from thedesign point of crystal structure for highly efficient hydrogen evolutionis promising but still challenging. In this study, we propose a chemicalcosubstitution strategy using the classic BiOIO₃ with anAurivillius-related crystal structure as the parent structure, wheresynergistic substitution of O^2–/IO₃^– with F^–/SeO₃^2– yields a macroscopic polarizable piezocatalyst, bismuth selenitefluoride BiFSeO₃. Systematic morphological engineeringtuned by mechanical ball milling (1–4 h) revealed a volcano-shapedstructure–activity relationship between H₂ evolutionactivity and milling duration, with the 3-h milled sample (e.g., BiFSeO₃-3 nanosheets) achieving the maximum rate of 1.059 mmol·g^–1 h^–1. Furthermore, mechanistic investigationsintegrating PFM, EPR, and band theory confirm the enhanced piezoelectricproperties (d₃₃ = 196 pm V^–1) and strain-drivencharge separation pathways in BiFSeO₃-3 nanosheets.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9850–9858"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003395","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":"Toward an Ideal S = 1/2 Kagome Antiferromagnet and Quantum Spin Liquid Candidate through Selective Mg2+ Doping of Averievite","authors":"Ethan Lowe,&nbsp;Lewis Giannelli,&nbsp;Claire Wilson,&nbsp;Ursula B. Hansen,&nbsp;David Boldrin","doi":"10.1021/acs.chemmater.6c01631","DOIUrl":"10.1021/acs.chemmater.6c01631","url":null,"abstract":"<p>Quantum spin liquids (QSLs) are exotic states of matterwhere geometricfrustration and quantum fluctuations suppress conventional magneticorder. S = 1/2 kagome antiferromagnets (KAFMs) are an ideal platformfor realizing such behavior, and several mineral-inspired Cu²⁺-based kagome systems have emerged as promising candidates. Amongthese, Averievite (Cu₅V₂O₁₀CsCl)offers a structurally distinct route to frustrated magnetism throughits copper oxovanadate framework, which hosts alternating kagome andhoneycomb layers. Prior studies have shown that targeted Zn²⁺ substitution on the honeycomb Cu_H site can suppress magneticorder and promote QSL-like behavior. Here we investigate Mg²⁺ substitution in the Averievite family, motivated by the geometricflexibility and favorable scattering contrast of Mg²⁺ relativeto Zn²⁺, the previously explored diamagnetic dopant. Hereinwe present the novel Mg_<em>x</em>Cu_{5–<em>x</em>}V₂O₁₀CsCl (<em>x</em> = 0, 0.5, 1, 2) family, utilizing X-ray diffraction, single-crystalelectron diffraction, and SQUID magnetometry to obtain precise structuralparameters, including site occupancies, antisite disorder, and localcoordination information, and to correlate these with the varied magneticbehavior. Increasing Mg²⁺ content leads to a pronouncedsuppression of both the structural and long-range magnetic ordering,alongside an increased mean field antiferromagnetic interaction, signalingenhanced magnetic frustration. Crucially, electron diffraction datais indicative of less than 1% Mg²⁺ antisite disorder ontothe kagome lattice in the Mg₂ compound. This contrastswith Zn-based analogues, preserving the integrity of the S = 1/2 kagomenetwork. At <em>x</em> = 2, neither long-range order nor spinfreezing is observed down to 2K, giving a new S = 1/2 KAFM with earlyhallmarks of QSL behavior and establishing Mg-doped Averievite asa clean and highly tunable platform for exploring QSL ground states.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10085–10094"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049481","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":"Mechanical Robustness in Fused Polyhedral Borane Crystals through Persistent Weak Intermolecular Interactions","authors":"Amit Mondal,&nbsp;Deepak Kumar Patel,&nbsp;Prabhat Karmakar,&nbsp;Jan Macháček,&nbsp;Ilaksh Adlakha,&nbsp;Tomas Base,&nbsp;Sundargopal Ghosh,&nbsp;Pijush Ghosh,&nbsp;Thalappil Pradeep","doi":"10.1021/acs.chemmater.6c01961","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01961","url":null,"abstract":"<p>Boraneclusters represent a unique class of molecular materialsfeaturing electron-deficient bonding and diverse polyhedral architectures.While their electronic, photophysical, and chemical properties havebeen extensively explored, the influence of polyhedral architectureon their mechanical behavior remains largely unknown. Here, we investigatethe nanomechanical properties of two prototypical-docosahydrooctadecaboraneisomers (<em>syn</em>-B₁₈H₂₂ and <em>anti</em>-B₁₈H₂₂) through nanoindentationexperiments, density functional theory (DFT) calculations, crystallographicand energy-framework analyses. The crystals exhibit exceptional mechanicalrobustness, displaying elastic modulus (<em>E</em>) of ∼20GPa for <em>syn</em>-B₁₈H₂₂ (<em><strong>syn</strong></em> <strong>-B</strong>_{<strong>18</strong>}) and ∼17 GPa for <em>anti</em>-B₁₈H₂₂ (<em><strong>anti</strong></em> <strong>-B</strong>_{<strong>18</strong>}), despite being composed exclusively of boron andhydrogen atoms and lacking conventional strong hydrogen-bonding networks.Structural analyses reveal that both isomers adopt three-dimensionalinterlocked packing arrangements sustained by multiple <em>B</em>···<em>μH</em>BB, B-<em>H</em>···<em>B</em>, and <em>B</em>···<em>B</em> contacts. In contrast, the parent single-polyhedral boranecrystal of B₁₀H₁₄ exhibits a substantially lowerelastic modulus (∼9 GPa) and has lower-dimensional interactionnetworks in the solid state. The structure-mechanical property correlationpresented here establishes a clear relationship between polyhedralarchitecture, intermolecular interaction topology, and mechanicalperformance in borane molecular crystals. More broadly, this workidentifies macropolyhedral fusion as a structural design strategyfor enhancing the mechanical robustness of cluster-based molecularsolids and expands the emerging materials chemistry of borane-derivedcrystalline materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10259–10270"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173890","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":"Alkali Manganese Oxynitridophosphates A1.1Mn2.9P3O8N2 (A = Li, Na): Direct Synthesis, Crystal Chemistry, and Ion-Transport Limitations","authors":"Agnieszka Wizner,Francisco Bonilla,Jian Xiang Lian,Juan-Miguel López del Amo,Gaizka Alcuten,François Fauth,Maxim Avdeev,Marcel Risch,Damien Saurel,Javier Carrasco,Michel Armand,Montse Casas-Cabanas,Marine Reynaud","doi":"10.1021/acs.chemmater.6c02114","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02114","url":null,"abstract":"Alkali manganese oxynitridophosphates A1.1Mn2.9P3O8N2 (A = Na, Li) were prepared by one-step solid-state ammonolysis, where the lithium analogue is obtained directly rather than by alkali-ion exchange from the sodium compound. Both compositions crystallize in a previously unreported orthorhombic Pbcn framework, in which ordered O/N environments, unusual manganese coordination in MnO5N and MnO6N2 polyhedra, and alkali–manganese disorder are accommodated within the same structure. The proposed structural model is supported by complementary synchrotron X-ray and neutron powder diffraction, electron microscopy, solid-state NMR and XAS data, as well as density functional theory calculations. Magnetic susceptibility is consistent with predominantly Mn2+ and antiferromagnetic ordering below 35.1 K for the Li phase and 32.6 K for the Na phase. Although the Mn2+/Mn3+ redox couple lies within the accessible potential window of nonaqueous M-ion batteries, reversible alkali extraction is limited by the restricted migration pathways imposed by the framework. Overall, this work expands the compositional and structural landscape of oxynitridophosphates and highlights nitrogen incorporation in phosphate crystal chemistry as a route to unconventional coordination environments, new framework connectivities and functional properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152039","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":"Metastable\u0000Inorganic Materials through Reactive Molten-Salt\u0000Ion Exchange","authors":"Sarah L. Ko,A. Elena Sjoblom,Kent J. Griffith","doi":"10.1021/acs.chemmater.6c01779","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01779","url":null,"abstract":"Abstract Material discovery is the foundational process for fundamental investigations and useful applications of functional and structural materials. It is the prerequisite for all downstream processes including property determination, synthetic optimization and scale-up, doping, defect engineering, morphology control, and surface and interfacial tuning. Through extensive experimental and, more recently, computational exploration, the number of yet-to-be-discovered thermodynamically stable compounds in low-order phase spaces has rapidly shrunk. However, new materials are needed to foster advances in established and emerging applications, particularly those related to energy storage, conversion, and efficiency. Thinking beyond equilibrium phase diagrams, a much larger phase space of metastable compounds exists if such phases can be synthetically accessed. This Perspective highlights the role of reactive molten-salt ion exchange (MSIX) as a technique for metastable inorganic material discovery. We discuss the thermodynamics, kinetics, crystal chemistry, and atomic-scale characterization of reactive molten-salt ion exchange. Emergent phenomena in ion exchange such as interdiffusion and the mixed-ion effect and challenges associated with characterizing mixed-ion and heterogeneous systems receive extra attention. In consideration of the breadth of MSIX, fundamental principles and general reaction schemes are used where possible with specific examples extensively referenced. MSIX is contextualized by comparisons to adjacent fields that involve molten salts, ion transport, and metastable materials. Opportunities and missed opportunities associated with computational approaches to molten-salt reactions and metastable materials are discussed. Unique prospects for in situ diffraction and NMR crystallography are highlighted along with future directions, including extensions to solid-state ion exchange (SSIX).","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209749","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}