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Understanding the Structure–Performance Relationship for Organic Thin-Film Transistors Using Liquid-Crystalline Organic Semiconductors 基于液晶有机半导体的有机薄膜晶体管结构与性能关系的研究
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-24 DOI: 10.1021/acs.chemmater.6c01989
Takayuki Oka, Nobutaka Shioya, Hiroki Nakano, Hiroaki Iino, Takeshi Hasegawa
{"title":"Understanding the Structure–Performance Relationship for Organic Thin-Film Transistors Using Liquid-Crystalline Organic Semiconductors","authors":"Takayuki Oka,&nbsp;Nobutaka Shioya,&nbsp;Hiroki Nakano,&nbsp;Hiroaki Iino,&nbsp;Takeshi Hasegawa","doi":"10.1021/acs.chemmater.6c01989","DOIUrl":"10.1021/acs.chemmater.6c01989","url":null,"abstract":"<p>Liquid-crystalline organic semiconductors are rapidlygaining attentionas next-generation materials for organic field-effect transistors(OFETs) due to their high charge mobility and thermal durability.However, thermal treatment at temperatures exceeding the transitionpoint of the liquid-crystalline phase degrades device performance,and the relationship between structure and performance remains unclear.In the present study, we investigate 2-decyl-7-phenyl-[1]benzothieno[3,2-<em>b</em>][1]benzothiophene, which exhibits outstanding charge-carriertransport properties among liquid-crystalline organic semiconductors.The aggregation structure in thin films is analyzed by combining X-raydiffraction, infrared spectroscopy, and atomic force microscopy, dependingon the heating conditions. Meanwhile, the OFET mobility is measuredin comparison with this structure. A comparative analysis identifiescrystallographic and conformational disorders responsible for thedegradation in OFET performance. This is due to the fact that, evenafter cooling to room temperature, flipped molecules resulting fromthe liquid-crystalline phase transition partially remain in the polycrystallinefilm. In other words, the OFET mobility of liquid-crystalline organicsemiconductors is governed by the film crystallinity, for which theconformational ordering of the alkyl side chains is a prerequisitebut not a sufficient condition. The results demonstrate a clear structure–performancerelationship in liquid-crystalline organic semiconductors, thus facilitatingthe fabrication of high-mobility OFET devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10298–10307"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049207","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}
引用次数: 0
Role of Ligand-to-Metal Charge Transfer in Anionic Redox Activity of the Layered Oxide Cathode for Na-Ion Batteries 配体-金属电荷转移在钠离子电池层状氧化物阴极阴离子氧化还原活性中的作用
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c00365
Abhinanda Sengupta, Amreen Bano, Kritika Thapliyal, Aakash Ahuja, Sri Harsha Akella, Malachi Noked, Dan T. Major, Sagar Mitra
{"title":"Role of Ligand-to-Metal Charge Transfer in Anionic Redox Activity of the Layered Oxide Cathode for Na-Ion Batteries","authors":"Abhinanda Sengupta,&nbsp;Amreen Bano,&nbsp;Kritika Thapliyal,&nbsp;Aakash Ahuja,&nbsp;Sri Harsha Akella,&nbsp;Malachi Noked,&nbsp;Dan T. Major,&nbsp;Sagar Mitra","doi":"10.1021/acs.chemmater.6c00365","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00365","url":null,"abstract":"<p>Developing high-performance cathode materials is crucialfor advancinggrid-scale sodium-ion batteries (SIBs). Here, we introduce a P2-typelayered oxide cathode material, Na<sub>0·67</sub>Ni<sub>0·33</sub>Mn<sub>0·51</sub>Ru<sub>0·16</sub>O<sub>2</sub>, whichdemonstrates exceptional electrochemical performance through a robustdual cationic–anionic redox mechanism. This material deliversa high discharge capacity of 175.6 mAh g<sup>−1</sup> at anaverage voltage of 3.6 V and maintains remarkable cycling stabilitywith ∼93% capacity retention after 1000 cycles. A key to thisperformance is the strategic Ru doping, which plays a pivotal rolein electronically stabilizing the oxidized oxygen states. By mediatingthe reversible formation of oxygen holes and preventing oxygen undercoordination,the Ru dopant stabilizes the anionic redox process. Unlike Na-richlayered oxides, this ligand-to-metal charge-transfer mechanism effectivelysuppresses detrimental oxygen evolution and preserves the structuralintegrity of the layered Na-deficient P2-type framework. This designstrategy enables a synergistic redox landscape, confirmed by <em>ex situ</em> and <em>operando</em> advanced characterizationsand theoretical calculations such as Fukui functions, offering criticalinsights into the rational design of high-capacity cathode for next-generationSIBs.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9763–9781"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173379","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}
引用次数: 0
Halide-Driven Stabilization of a Hexagonal Polymorph with a Distinct and Disordered Li Substructure in Li3.25GeS3.25Cl0.75 Li3.25GeS3.25Cl0.75中具有明显无序Li亚结构的六方晶型的卤化物驱动稳定
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c01317
Hyeonjin Seo, Alicia Manjón-Sanz, Seung-Tae Hong
{"title":"Halide-Driven Stabilization of a Hexagonal Polymorph with a Distinct and Disordered Li Substructure in Li3.25GeS3.25Cl0.75","authors":"Hyeonjin Seo,&nbsp;Alicia Manjón-Sanz,&nbsp;Seung-Tae Hong","doi":"10.1021/acs.chemmater.6c01317","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01317","url":null,"abstract":"<p>Targeted halide substitution provides an effective routeto accessstructural motifs in thio-LISICON systems. Here, partial substitutionof S<sup>2–</sup> by Cl<sup>–</sup> in Li<sub>4</sub>GeS<sub>4</sub> stabilizes a hexagonal polymorph near the compositionLi<sub>3.25</sub>GeS<sub>3.25</sub>Cl<sub>0.75</sub>. Ab initio structuredetermination by joint refinement of time-of-flight neutron powderdiffraction and X-ray diffraction data supports a <em>P</em>6<sub>3</sub><em>mc</em> average structure built on a hexagonalclose-packed anion framework. The resulting framework exhibits a distinctLi-site topology with symmetry-inequivalent Li environments, includinga shared tetrahedral framework site and additional tetrahedral andoctahedral interstitial sites. Systematic investigation of the Li<sub>4–<em>x</em></sub>GeS<sub>4–<em>x</em></sub>Cl<sub><em>x</em></sub> series shows that the hexagonalphase is preferentially stabilized near the nominal <em>x</em> = 0.75 composition, for which no secondary crystalline phase wasdetected by PXRD. Structural analysis indicates that halide substitutionproduces a rearranged and partially disordered Li substructure. Bond-valenceenergy landscape calculations show that the computed Li-energy topologyis highly sensitive to the representation of Li/Ge occupational disorder,with a Ge-free sensitivity model recovering the crystallographic Li1-relatedminimum and markedly altering the calculated percolation topology.Li<sub>3.25</sub>GeS<sub>3.25</sub>Cl<sub>0.75</sub> exhibits a room-temperatureionic conductivity of 3.91 × 10<sup>–6</sup> S cm<sup>–1</sup>. These results demonstrate that halide substitutioncan stabilize hexagonal polymorphs and reorganize the Li substructurein sulfide solid electrolytes, providing a platform for examininghow structural disorder and Li-site topology influence ion transport.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9929–9938"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173438","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}
引用次数: 0
Metal-Site Chemistry Dominates Carrier Recombination in Layered Halide Perovskites: Insights from Excited-State Dynamics and Interpretable Machine Learning 层状卤化物钙钛矿中的载流子复合由金属位化学主导:来自激发态动力学和可解释机器学习的见解
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-08-18 DOI: 10.1021/acs.chemmater.6c01097
Nikhil Singh, Dibyajyoti Ghosh
{"title":"Metal-Site Chemistry Dominates Carrier Recombination in Layered Halide Perovskites: Insights from Excited-State Dynamics and Interpretable Machine Learning","authors":"Nikhil Singh,&nbsp;Dibyajyoti Ghosh","doi":"10.1021/acs.chemmater.6c01097","DOIUrl":"10.1021/acs.chemmater.6c01097","url":null,"abstract":"<p>Layered halide perovskites (LHPs)offer a powerful platformtoprecisely engineer excited-state carrier dynamics and optoelectronicperformance via compositional tuning of B-site metals. Here, we contrastprototypical lead-based (BA)<sub>2</sub>PbBr<sub>4</sub> with itsdouble-perovskite analogue (BA)<sub>4</sub>AgBiBr<sub>8</sub> to isolatethe role of B-site chemistry in dictating photoactivity in these emerginglayered semiconductors. Nonadiabatic molecular dynamics integratedwith interpretable machine learning models reveal the detailed impactof time-dependent structural distortions on the instantaneous electronicstructures in these LHPs. The alternating [AgBr<sub>6</sub>]<sup>5–</sup> and [BiBr<sub>6</sub>]<sup>3–</sup> octahedral arrangementin (BA)<sub>4</sub>AgBiBr<sub>8</sub> gives rise to intrinsicallystronger structural fluctuations and enhanced electron–phononcoupling, leading to faster nonradiative recombination than that ina more rigid Pb-based framework. Extensive SHapley Additive exPlanationsanalyses further depict that the thermally driven octahedral distortionsin the [AgBiBr<sub>8</sub>]<sup>4+</sup> layers exert the strongestcontrol over excited-state charge dynamics at ambient conditions.The intrinsic structural anisotropy in adjacent Ag/Bi-centered octahedrastrengthens electron–phonon coupling, activating nonradiativerecombination channels and consequently suppressing the photoluminescence.Our findings establish a mechanistic link among inorganic sublatticecomposition, structural dynamics, and carrier lifetimes, presentingkey design principles to realize high-performing lead-free LHPs foroptoelectronics.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9829–9838"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148767196","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}
引用次数: 0
Molecularly Engineered Dual-Network Polydimethylsiloxane Composites with Recoverable Thermal Transport and Low Contact Thermal Resistance 具有可回收热传递和低接触热阻的分子工程双网络聚二甲基硅氧烷复合材料
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-15 DOI: 10.1021/acs.chemmater.6c01568
Jianan Song, Guangxing Huang, Feng Wei, Haidong Gu, Dayong Chen, Beibei Chen, Kan Zhang
{"title":"Molecularly Engineered Dual-Network Polydimethylsiloxane Composites with Recoverable Thermal Transport and Low Contact Thermal Resistance","authors":"Jianan Song,&nbsp;Guangxing Huang,&nbsp;Feng Wei,&nbsp;Haidong Gu,&nbsp;Dayong Chen,&nbsp;Beibei Chen,&nbsp;Kan Zhang","doi":"10.1021/acs.chemmater.6c01568","DOIUrl":"10.1021/acs.chemmater.6c01568","url":null,"abstract":"<p>Thermal interface materials (TIMs) require both efficientheattransfer, reliable interfacial contact, and long-term damage tolerance,yet highly filled polymer composites often suffer from poor deformability,irreversible interfacial damage, and increased contact thermal resistance.Herein, a dual-network self-healing polydimethylsiloxane (SH-PDMS)matrix was designed using a dual-functional cross-linker that integratespermanent covalent cross-links with reversible Diels–Alder(DA) dynamic bonds. The permanent network provided structural stability,while the reversible DA bonds enabled thermally triggered networkrearrangement and self-healing. Thermally conductive composites containingAl<sub>2</sub>O<sub>3</sub>, boron nitride, and ZnO/carbon fiber fillerswere further prepared to examine how filler architecture affects self-healingbehavior, recoverable thermal transport, and interfacial contact thermalresistance. Among the tested composites, ZnO/carbon fiber/SH-PDMSachieved the highest thermal conductivity of 2.5 W·m<sup>–1</sup>·K<sup>–1</sup> owing to the formation of long-rangeconductive pathways and local thermal bridges. After mechanical damage,the thermal conductivity of all composites decreased substantiallybut recovered to more than 90% of the original value after healing,demonstrating efficient restoration of disrupted heat-transfer pathways.Notably, the thermal conductivity recovery was much higher than thecorresponding mechanical recovery, indicating that heat-transfer restorationdoes not require complete recovery of the load-bearing network. Thethermally treated SH-PDMS-based TIMs also exhibited reduced contactthermal resistance under mild pressure, with ZnO/carbon fiber/SH-PDMSreaching 0.205 K·cm<sup>2</sup>·W<sup>–1</sup> at70 psi. In an LED–TIM–heat sink assembly, the ZnO/carbonfiber/SH-PDMS TIM reduced the maximum LED temperature from 68.1 °Cto 51.8 °C. These results demonstrate that the dual-network SH-PDMSmatrix provides a promising route for self-healing TIMs with recoverablethermal transport and low contact thermal resistance.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10050–10061"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973826","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}
引用次数: 0
Toward Fluorine-Free Electrolytes: Physicochemical Properties and Ionic Interactions in Acesulfame-Based Ionic Electrolytes 迈向无氟电解质:安赛蜜基离子电解质的理化性质和离子相互作用
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-17 DOI: 10.1021/acs.chemmater.6c01883
Wern Huay Mah, Jhonatan Soto Puelles, Julius Tiongson, Luke A. O’Dell, Fangfang Chen, Jennifer M. Pringle
{"title":"Toward Fluorine-Free Electrolytes: Physicochemical Properties and Ionic Interactions in Acesulfame-Based Ionic Electrolytes","authors":"Wern Huay Mah,&nbsp;Jhonatan Soto Puelles,&nbsp;Julius Tiongson,&nbsp;Luke A. O’Dell,&nbsp;Fangfang Chen,&nbsp;Jennifer M. Pringle","doi":"10.1021/acs.chemmater.6c01883","DOIUrl":"10.1021/acs.chemmater.6c01883","url":null,"abstract":"<p>Fluorine-freeionic liquids and salts are attracting growing interestas safer and more sustainable electrolyte components for Li-ion batteries,addressing both the flammability of conventional carbonate-based electrolytesand the environmental persistence of fluorinated anions. This motivatesthe use of the nonfluorinated acesulfame (ACE<sup>–</sup>)anion, derived from potassium acesulfame, a toxicologically evaluatedtabletop sweetener. Further, ether-functionalized cations may facilitatelithium-ion transport by promoting favorable lithium coordinationenvironments. Here, two ionic electrolytes were prepared by combiningthe ACE<sup>–</sup> anion with either the cyclic-ether <em>N</em>-ethyl-<em>N</em>-methyloxazolidinium (C<sub>2</sub>moxa<sup>+</sup>) cation or the <em>N</em>-methoxy-<em>N</em>,<em>N</em>,<em>N</em>-trimethylammonium(N<sub>111(1O1)</sub><sup>+</sup>) cation, where the ether is functionalizedon the side chain, and lithium acesulfame (Li-ACE) to evaluate theirpromise as battery electrolytes. The thermal and transport propertiesand the ion dynamics were studied and compared at various Li-ACE concentrations.Among all the lithium-based electrolyte systems, [N<sub>111(1O1)</sub>][ACE] containing 10 mol % Li-ACE exhibited the highest conductivity,reaching 5.4 × 10<sup>–4</sup> S cm<sup>–1</sup> at 50 °C. However, [C<sub>2</sub>moxa][ACE] exhibited a higherLi<sup>+</sup> diffusivity ratio at both 20 and 50 mol % Li-ACE content,indicating that the cyclic ether oxygen may create a distinct localchemical environment that facilitates greater relative mobility ofLi<sup>+</sup>. Additionally, the Li<sup>+</sup> solvation environmentin acesulfame-based electrolytes was elucidated using combined experimentaland simulation approaches. In both electrolytes, Li<sup>+</sup> wasfound to coordinate with ACE<sup>-</sup> through the nitrogenatom as well as the sulfonyl and carbonyl oxygens. Moreover, moleculardynamics simulations suggest that smaller Li–Li clusters wereformed in [C<sub>2</sub>moxa][ACE] electrolytes compared to [N<sub>111(1O1)</sub>][ACE], which may contribute to the enhanced Li<sup>+</sup> mobility compared with ACE<sup>–</sup> in [C<sub>2</sub>moxa][ACE] electrolytes at 20 and 50 mol %. These results indicatethat cation chemistry plays an important role in tuning Li<sup>+</sup> solvation structure, ion clustering, and ion transport.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10185–10201"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148984951","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}
引用次数: 0
Suppressing Second-Order Jahn–Teller Distortion of Bi3+ by Smaller Y3+-Substitution in Bi3O4Cl 用较小的Y3+取代Bi3O4Cl抑制Bi3+的二阶Jahn-Teller畸变
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-21 DOI: 10.1021/acs.chemmater.6c01862
Kosei Takano, Kanta Ogawa, Takafumi Yamamoto
{"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 Y<sup>3+</sup> sitein layered Bi<sub>2</sub>YO<sub>4</sub>Cl can serve as a structuraltemplate to stabilize a centrosymmetric coordination environment forBi<sup>3+</sup> (up to 40% replacement), effectively suppressing theSOJT distortion. In this study, we re-examined the synthesis processof Bi<sub>2</sub>(Y<sub>1–<em>x</em></sub>Bi<sub><em>x</em></sub>)O<sub>4</sub>Cl 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 Bi<sub>3</sub>O<sub>4</sub>Cl rather than a Bi-substitutedBi<sub>2</sub>YO<sub>4</sub>Cl. 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}
引用次数: 0
COFFlow: Building-Block-Based Generative Modeling for Two-Dimensional Covalent Organic Framework Discovery 基于构建块的二维共价有机框架发现生成模型
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-23 DOI: 10.1021/acs.chemmater.6c01524
Yuanhui Pan, Yunrui Yan, Cheng Zeng, Jirui Jin, Mingjie Liu
{"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}
引用次数: 0
Nucleation and Coalescence of Wüstite-like Motifs in Oxygen-Deficient Magnetite: A Deep-Potential Molecular Dynamics Study 缺氧磁铁矿中wite -like motif的成核和聚结:深电位分子动力学研究
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c02276
Zeng Liang, Kejiang Li, Jianliang Zhang, Alberto N. Conejo
{"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 Fe<sub>3</sub>O<sub>4</sub> 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<sub>1–x</sub>O 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}
引用次数: 0
Integrated Systems for Self-Powered Sensing and Closed-Loop Therapy 自供电传感和闭环治疗集成系统
IF 7.1 2区 材料科学
Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c02528
Futing Wang, Dan Yang, Ren Cai
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