Chemistry of Materials最新文献

Anticreep and Antiswelling Sensor Hydrogel Inspired by Human Pressure Tactile for Food Detection 受人体压力触觉启发的抗爬行和抗膨胀传感器水凝胶用于食品检测

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-02 DOI: 10.1021/acs.chemmater.5c01053

Qinqin Cui, Yao Li, Wanqi Li, Cong Wang, Sheng Cheng, Xu Fei, Longquan Xu

{"title":"Anticreep and Antiswelling Sensor Hydrogel Inspired by Human Pressure Tactile for Food Detection","authors":"Qinqin Cui, Yao Li, Wanqi Li, Cong Wang, Sheng Cheng, Xu Fei, Longquan Xu","doi":"10.1021/acs.chemmater.5c01053","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01053","url":null,"abstract":"Achieving biomimetic human pressure tactile perception for food detection has been a primary objective in the development of sensing hydrogels. However, the inherent challenges associated with the creeping and swelling behaviors of hydrogels have significantly impeded progress. In this study, we introduce a hydrogel system engineered with a multiscale energy dissipation structure to enable flexible sensing and detection that emulates human pressure tactile. At the molecular scale, the supramolecular interactions, including hydrogen bonding and ionic interactions among macromolecular segments, are incorporated into the hydrogel matrix. At the nanoscale, an elastic spherical mesh structure is integrated to reinforce the hydrogel network. When subjected to external forces, the hydrogel effectively resists creep by absorbing external forces and storing energy. The PAASi hydrogels exhibit remarkable creep resistance (withstanding 1000 compression cycles without deformation), swelling resistance (no volume change after soaking), and high sensitivity (1.16 kPa–1). The sensing systems utilizing PAASi hydrogels have been successfully applied to evaluate the freshness of fruits and the water content in sea cucumbers. This work has guiding significance for irritant response hydrogels in food detection.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204055","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

Dynamically Switchable Room Temperature Phosphorescence in Two-Coordinate Carbene-Metal-Amide Complexes via Mediation by Charge-Transfer States 电荷转移态介导的二坐标碳-金属-酰胺配合物室温磷光动态切换

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-02 DOI: 10.1021/acs.chemmater.5c02124

Zanis Sisojevs, Armands Ruduss, Fatima Zohra Boudjenane, Sergey Belyakov, Kaspars Traskovskis

{"title":"Dynamically Switchable Room Temperature Phosphorescence in Two-Coordinate Carbene-Metal-Amide Complexes via Mediation by Charge-Transfer States","authors":"Zanis Sisojevs, Armands Ruduss, Fatima Zohra Boudjenane, Sergey Belyakov, Kaspars Traskovskis","doi":"10.1021/acs.chemmater.5c02124","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02124","url":null,"abstract":"Due to a weak spin–orbit coupling (SOC) seen in the majority of organic room temperature phosphorescence (RTP) emitters, their light emission profile embodies a substantial contribution from fluorescence, thus obstructing the visual perception of the phosphorescence signal. Here, we present an approach that allows tuning characteristics of organometallic RTP materials from fluorescence-dominated to fully phosphorescent. The investigation of a series of two-coordinate Cu(I), Ag(I), or Au(I)-based complexes bearing an amide-type acridone ligand and several carbene-type ligands with varied electrophilic properties reveals that the intersystem crossing (ISC) rate to the phosphorescent locally excited acridone triplet state (3LE) can be significantly increased if intermediate carbene-to-amide interligand charge-transfer (CT) states are populated during the photoexcitation process. At the same time, the compounds retain long phosphorescence lifetimes in the range of 1.5–73 ms. A purely phosphorescent complex 2-Au-Acr with a high photoluminescence quantum yield of 0.75 was obtained. By exploiting its susceptibility to O2-induced phosphorescence quenching, a dynamically on-and-off switchable phosphorescent polymer-emitter composite system is demonstrated, where the light emission can be controlled solely by the change in the excitation light intensity. The unique properties of the demonstrated complex open unexplored application directions of RTP materials, such as their use in luminescent light intensity sensors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"157 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203916","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

Investigation of 2,6-Sodium Naphthalene Dicarboxylate Structure–Reactivity Relationship by Operando X-ray Diffraction and Post-Mortem Transmission Electron microscopy 2,6-萘二羧酸钠结构-反应性关系的操作x射线衍射和透射电镜研究

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-02 DOI: 10.1021/acs.chemmater.5c01939

Maxandre Caroff, Nikhil Subash, Matthieu Becuwe, Carine Davoisne

引用次数: 0

Reactive Strand Extension to Improve Stretchability in Semiconducting Polymers 活性链延伸提高半导体聚合物的可拉伸性

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-02 DOI: 10.1021/acs.chemmater.5c01198

Shine H. Huang, Azalea Uva, Saroj Upreti, Adnan Sharif, Karen Fukuda, Rebecca A. Belisle, Xiaodan Gu, Helen Tran

{"title":"Reactive Strand Extension to Improve Stretchability in Semiconducting Polymers","authors":"Shine H. Huang, Azalea Uva, Saroj Upreti, Adnan Sharif, Karen Fukuda, Rebecca A. Belisle, Xiaodan Gu, Helen Tran","doi":"10.1021/acs.chemmater.5c01198","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01198","url":null,"abstract":"As electronics become more seamlessly integrated into our everyday lives, the demand for durable, stretchable, and electron-conducting materials will continue to grow. However, many conductive materials suffer from poor electrical performance under repeated mechanical strain, which limits their lifetime use. Inspired by developments to enhance stretchability in nonconjugated materials with covalent mechanochemistry, we explore reactive strand extension (RSE) as a strategy to mitigate poor electronic performance in conjugated polymer semiconductors under strain. Herein, we incorporated RSE into a donor–acceptor conjugated polymer by copolymerizing cinnamate dimers into the conjugated backbone and evaluated their impact on stretchability. RSE was found to improve stretchability in cross-linked conjugated polymer systems via crack onset strain measurements, atomic force microscopy, dichroic ratio measurements, and grazing-incidence wide-angle X-ray scattering. Lastly, charge carrier mobility measurements from organic field-effect transistors revealed that RSE-containing cross-linked conjugated polymers retained mobility more effectively under mechanical strain compared to unmodified conjugated polymers. Overall, our study presents an alternative strategy to improve the performance of conjugated polymers for stretchable electronics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203919","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

Quantitative Analysis of the Doping and Defect Density in Mixed Sn–Pb Perovskites Mediated by SnF2 SnF2介导的混合Sn-Pb钙钛矿掺杂和缺陷密度的定量分析

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-02 DOI: 10.1021/acs.chemmater.5c00816

Jasmeen Nespoli, Maartje J. van der Meer, Sander Heester, Jim S. Koning, Bart Boshuizen, L. Jan Anton Koster, Tom J. Savenije

{"title":"Quantitative Analysis of the Doping and Defect Density in Mixed Sn–Pb Perovskites Mediated by SnF2","authors":"Jasmeen Nespoli, Maartje J. van der Meer, Sander Heester, Jim S. Koning, Bart Boshuizen, L. Jan Anton Koster, Tom J. Savenije","doi":"10.1021/acs.chemmater.5c00816","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00816","url":null,"abstract":"Last year’s mixed Sn–Pb perovskites have been applied as low-bandgap absorbers in efficient solar cells. However, the performance is still limited by tin oxidation, resulting in doping and defects. Here we perform a quantitative analysis on how tin oxidation affects the optoelectronic properties of spin-coated Cs0.25FA0.75Sn0.5Pb0.5I3 with varying SnF2 additions ranging from 0 to 20 mol %. First, optical spectroscopy is used to determine the fraction of Sn4+ in the spin-coating solution, which varies depending on the purity of the starting SnI2 precursor. By applying steady-state microwave conductance, a large decrease in the dark conductivity from ∼100 to <∼1 S m–1 in the spin-coated films on going from 0 to 2 mol % SnF2 is observed. We conclude that, without SnF2, ∼12% of the Sn4+ in solution leads to mobile carriers in the form of free holes, p0, in the perovskite layer. Upon SnF2 addition, p0 decreases to <1 × 1016 cm–3. We infer that a ∼70 times excess of SnF2 over the initial concentration of Sn4+ in solution is required to scavenge the Sn4+ and obtain layers with reduced doping. Although the reduction of p0 and defects results in increased carrier lifetimes, higher SnF2 additions are also required to decrease the surface defects, leading to even longer lifetimes close to 200 ns. The reduced doping of these perovskite films with SnF2 makes them ideal candidates for efficient solar cells; however, SnF2 also induces compositional heterogeneity and accumulation of SnOx at the surface.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203976","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

Reductive Transformation of Imine Covalent Organic Frameworks into Emissive Polymers: Insights into Emission Quenching 亚胺共价有机框架的还原转化为发射聚合物：对发射猝灭的见解

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-01 DOI: 10.1021/acs.chemmater.5c01951

Agata Tyszka-Gumkowska, Mateusz Brzeziński, Sylwester Gawinkowski, Tomasz Polczyk, Wojciech Wegner, Mateusz Wlazło, Piotr Bernatowicz, Jan Nawrocki, Przemysław Gaweł, Krzysztof Noworyta, Jakub Ostapko

{"title":"Reductive Transformation of Imine Covalent Organic Frameworks into Emissive Polymers: Insights into Emission Quenching","authors":"Agata Tyszka-Gumkowska, Mateusz Brzeziński, Sylwester Gawinkowski, Tomasz Polczyk, Wojciech Wegner, Mateusz Wlazło, Piotr Bernatowicz, Jan Nawrocki, Przemysław Gaweł, Krzysztof Noworyta, Jakub Ostapko","doi":"10.1021/acs.chemmater.5c01951","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01951","url":null,"abstract":"Although imine-linked covalent organic frameworks (COFs) are readily synthesized, their lack of intrinsic emission constrains their potential in optoelectronic applications. Moreover, the underlying mechanisms governing excited-state energy dissipation remain poorly understood. To overcome these limitations, we present a straightforward strategy to transform nonemissive, anthracene-based imine-COFs (im-COF) into highly emissive amine-based covalent organic polymers (am-COP) through NaBH3CN/benzoic acid reduction, achieving solid-state emission quantum yields of up to 30%. To clarify the excited-state energy dissipation mechanisms in COFs and COPs, we synthesized molecular reference compounds featuring either imine or amine functionalities. Photophysical studies, supported by density functional theory (DFT) calculations, reveal that the excited states of both amines and imines exhibit weak charge transfer (CT) properties. Furthermore, a comparative analysis of the photophysical behavior of molecular references, im-COFs, and am-COPs demonstrates that the polymer emission arising from charge-transfer processes is modulated by the polymer’s intrinsic polarity. These findings provide fundamental insights into the photophysical behavior of COFs, thus paving the way for the development of emissive porous materials with promising advanced applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"157 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203911","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

β-Sheet Structures Enhance Aggregation-Induced Emission Signals in Peptide-Based Coacervates β-薄片结构增强肽基凝聚体中聚集诱导的发射信号

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-10-01 DOI: 10.1021/acs.chemmater.5c00705

Moumita Halder, Zhicheng Jin, Ke Li, Lubna Amer, Tengyu He, Suyeong Han, Xiang Zhong, Neal K. Devaraj, Jesse V. Jokerst

{"title":"β-Sheet Structures Enhance Aggregation-Induced Emission Signals in Peptide-Based Coacervates","authors":"Moumita Halder, Zhicheng Jin, Ke Li, Lubna Amer, Tengyu He, Suyeong Han, Xiang Zhong, Neal K. Devaraj, Jesse V. Jokerst","doi":"10.1021/acs.chemmater.5c00705","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00705","url":null,"abstract":"Phase-separating peptides (PSPs) are known to undergo liquid–liquid phase separation (LLPS) to produce coacervates with applications in bioimaging, drug delivery, and theranostics. However, the structure–function relationship of the peptide building blocks remains unclear. Here, we used an aggregation-induced emission reporter to study how different β-sheet promoters impact coacervation. We synthesized an anionic Asp-peptide (D10) and a cationic Arg-peptide (R10) covalently conjugated to tetraphenylethene pyridinium (PyTPE)─an aggregation-induced emission generator (AIEgen). We included several spacer units composed of β-sheet-promoting self-assembling peptides (F2G2, W2G2, FFVLK, and GFFYK) between the AIEgen and R10 and investigated their size and AIE intensities after coacervation. The properties of the coacervates vary with endogenous factors (peptide sequence, number of Arg and Asp residues, charge ratio, and total charge equivalent concentration of peptides), exogenous factors (pH, ionic strength, salts), and the β-sheet content of the constituting peptide. We observed that a minimum 10 mM phosphate buffer salt concentration, pH 4–12, total charge equivalent concentration of 0.8 mM, and charge ratio (R10/D10) of 0.5 are required for 100% peptide complexation. Peptides containing the FFVLK sequence exhibited the highest AIE (∼450-fold) with the capability to form self-coacervates in phosphate buffer. The W2G2 motif had negligible activation. Finally, we confirmed that the coacervates retain their shape after intracellularly labeling murine colon adenocarcinoma cells (MC38) via caveolae-mediated endocytosis with >95% cell viability.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"8 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203913","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

Oxidation-Induced Giant Resistivity Change Associated with Structural and Electronic Reconstruction in Layered Sr3Cr2O7−δ Epitaxial Thin Films 层状Sr3Cr2O7−δ外延薄膜氧化诱导的巨电阻率变化与结构和电子重构

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-09-30 DOI: 10.1021/acs.chemmater.5c00810

Zhaochen Ma, Daichi Oka, Shintaro Fukuda, Daisuke Shiga, Koichi Harata, Hiroshi Kumigashira, Tomoteru Fukumura

{"title":"Oxidation-Induced Giant Resistivity Change Associated with Structural and Electronic Reconstruction in Layered Sr3Cr2O7−δ Epitaxial Thin Films","authors":"Zhaochen Ma, Daichi Oka, Shintaro Fukuda, Daisuke Shiga, Koichi Harata, Hiroshi Kumigashira, Tomoteru Fukumura","doi":"10.1021/acs.chemmater.5c00810","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00810","url":null,"abstract":"Ruddlesden–Popper-type Sr3Cr2O7−δ (001) epitaxial thin films with high crystallinity and flat surfaces are grown by pulsed laser deposition. The as-grown thin films exhibit transparent color and high resistivity, indicating the existence of a number of oxygen vacancies as well as Cr3+ ions. Air annealing causes a nonmonotonic variation in lattice constants and a color change to brownish due to the compensation of ordered oxygen vacancies as well as oxidation of the Cr3+ ions to Cr4+ ions. At the same time, the room temperature resistivity shows a large decrease exceeding 5 orders of magnitude. Synchrotron-radiation photoemission spectroscopy reveals a wider Mott gap for the Cr3+ ions than that for Cr4+ ions. Accordingly, the giant resistivity change is attributed to the synergistic effects of dimensionality variation in the electron conduction pathway and band-structure modulation, which depends on the Cr valence within the layered structure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203914","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

Local Structure and Surface Acidity of Overlayers Prepared by Atomic Layer Deposition of Silica on Alumina 二氧化硅在氧化铝上原子层沉积制备覆层的局部结构和表面酸度

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-09-30 DOI: 10.1021/acs.chemmater.5c01832

Melis Yarar, Zixuan Chen, Diana Piankova, Matthias Becker, Alexander V. Yakimov, Christophe Copéret, Pierre Florian, Christoph R. Müller, Alexey Fedorov

{"title":"Local Structure and Surface Acidity of Overlayers Prepared by Atomic Layer Deposition of Silica on Alumina","authors":"Melis Yarar, Zixuan Chen, Diana Piankova, Matthias Becker, Alexander V. Yakimov, Christophe Copéret, Pierre Florian, Christoph R. Müller, Alexey Fedorov","doi":"10.1021/acs.chemmater.5c01832","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01832","url":null,"abstract":"Understanding the structure of the silica–alumina interface and the reactivity of such interfacial sites in amorphous aluminosilicate (ASA) materials is essential due to their industrial utilization as solid acid catalysts. Here, we link the structure of silica layers grown on alumina by atomic layer deposition (ALD) to the acidic and catalytic properties of ASA. In particular, we study the local structure of silica overlayers as a function of the number of ALD cycles applied and reveal how the coordination environment of Al and Si sites governs the Lewis and Bro̷nsted acidity and catalytic activity using methanol dehydration as a model structure-sensitive reaction. Relying on advanced solid-state NMR characterization, including 27Al{29Si} dipolar heteronuclear multiple-quantum coherence (D-HMQC) and 29Si{27Al} dipolar-mediated refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) experiments, dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS), and infrared spectroscopy using probe molecules (CO, pyridine), we demonstrate that the atomic-scale mixing of silica and alumina generates strong Bro̷nsted acidity and increases the strength of the Lewis acid sites. Our findings indicate that the density of acid sites is closely related to the coverage of the alumina surface by silica and can be controlled by the number of ALD cycles applied. This study advances our understanding of the relationship between the local environment of Si and Al sites, the abundance and strength of acid sites, and the superior high-temperature selectivity of SiOx-Al2O3-based catalysts in methanol dehydration when compared to unmodified alumina.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203922","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

Phase Stability and Transformations in Lead Mixed Halide Perovskites from Machine Learning Force Fields 基于机器学习力场的铅混合卤化物钙钛矿的相稳定性和相变

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-09-30 DOI: 10.1021/acs.chemmater.5c01730

Xia Liang, Johan Klarbring, Aron Walsh

{"title":"Phase Stability and Transformations in Lead Mixed Halide Perovskites from Machine Learning Force Fields","authors":"Xia Liang, Johan Klarbring, Aron Walsh","doi":"10.1021/acs.chemmater.5c01730","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01730","url":null,"abstract":"Lead halide perovskites (APbX3) offer tunable optoelectronic properties, but feature an intricate phase stability landscape. Here, we employ on-the-fly data collection and an equivariant message-passing neural network potential to perform large-scale molecular dynamics of three prototypical lead mixed-halide perovskite systems: CsPbX3, MAPbX3, and FAPbX3. Integrating these simulations with the PDynA structure analysis toolkit, we resolve both equilibrium phase diagrams and the dynamic structural evolution under varying temperatures and halide mixtures. Our findings reveal that A-site cations strongly modulate tilt modes and phase pathways: MA+ effectively “forbids” the β-to-γ transition in MAPbX3 by requiring extensive molecular rearrangements and crystal rotation, whereas the debated low-temperature phase in FAPbX3 is predicted to be best represented as an Im3̅ (a+a+a+) cubic phase. Additionally, small changes in halide composition and arrangement, from uniform mixing to partial segregation, alter octahedral tilt correlations. Segregated domains can even foster anomalous tilting modes that impede uniform phase transformations. These results highlight the multiscale interplay between the cation environment and halide distribution, offering a route for tuning perovskite architectures toward improved phase stability and control.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"3 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203925","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