Chemistry of Materials最新文献_第8页

The Importance of Nanoscale Phenomena in Electrolyte Behavior: Acetonitrile-Aqueous Zinc Sulfate Electrolytes 纳米级现象在电解质行为中的重要性：乙腈-硫酸锌水溶液电解质

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-12 DOI: 10.1021/acs.chemmater.6c01065

Emma N. Antonio,Luis Kitsu Iglesias,Kee Sung Han,Michael Counihan,Stefan Ilic,Mrinal K. Bera,Julian Mars,Karl T. Mueller,Sanja Tepavcevic,Michael F. Toney

{"title":"The Importance of Nanoscale Phenomena in Electrolyte Behavior: Acetonitrile-Aqueous Zinc Sulfate Electrolytes","authors":"Emma N. Antonio,Luis Kitsu Iglesias,Kee Sung Han,Michael Counihan,Stefan Ilic,Mrinal K. Bera,Julian Mars,Karl T. Mueller,Sanja Tepavcevic,Michael F. Toney","doi":"10.1021/acs.chemmater.6c01065","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01065","url":null,"abstract":"Electrolytes composed of mixed solvents are of significant scientific and technological importance in lithium-ion and beyond-lithium-ion batteries, and more broadly across physical chemistry. Their emergence has highlighted the importance of multiscale phenomena, particularly the development of nanoscale solution heterogeneities. It is therefore essential to assess how these inhomogeneities and nanoscale aggregates influence solvation, transport, and electronic properties. Here we investigate the solution structure and transport properties of aqueous zinc sulfate electrolytes with acetonitrile (ACN) additives, where the addition of ACN leads to improved cyclability. Using complementary anomalous small-angle X-ray scattering, X-ray pair distribution function, electrochemistry, and NMR, we identify the presence of salt-rich-water-rich and salt-poor-ACN-rich nanoheterogeneities and, at higher ACN concentrations, liquid–liquid phase separation. We find that the size of zinc sulfate ion clusters in the water domains increases slightly upon ACN addition, while the ACN-rich domains grow much larger as phase separation is approached. The inverse Haven ratio, determined using the ionic conductivity and diffusivity, is much less than unity and decreases slightly upon addition of ACN, which shows ion–ion interactions. We speculate that the increased ion–ion interactions with increased ACN are a result of a reduction in free water, the increase in zinc sulfate cluster size, and/or an increase in solution tortuosity. This work highlights key phenomena to consider when engineering new water-organic-salt electrolyte systems and establishes a phase diagram for water–ACN–ZnSO4 that can guide advances, such as self-adaptive electrolytes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"471 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152042","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

Alcohol-Mediated Area-Selective Atomic Layer Deposition through Surface Chemical States Modulation 通过表面化学态调制醇介导的区域选择性原子层沉积

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-12 DOI: 10.1021/acs.chemmater.6c01198

Weizhen Wang,Boxuan Li,Kun Cao,Zilian Qi,Eryan Gu,Yanwei Wen,Bin Shan,Rong Chen

{"title":"Alcohol-Mediated Area-Selective Atomic Layer Deposition through Surface Chemical States Modulation","authors":"Weizhen Wang,Boxuan Li,Kun Cao,Zilian Qi,Eryan Gu,Yanwei Wen,Bin Shan,Rong Chen","doi":"10.1021/acs.chemmater.6c01198","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01198","url":null,"abstract":"Area-selective atomic layer deposition (AS-ALD) fundamentally relies on a distinct disparity in surface chemical states between growth and nongrowth area. For SiO2/Cu patterned architectures, the oxidation of the Cu surface serves as a primary driver for the loss of selectivity as the ALD process proceeds. Herein, an alcohol-mediated AS-ALD process is proposed, utilizing alcohols with varying carbon chain lengths to precisely modulate surface chemical states to enhance selectivity of AS-ALD WOx film. A competitive-synergistic mechanism involving surface reductive capability and steric hindrance is identified as the governing factor for process selectivity. Results demonstrate that while the reducing ability of alcohols on oxidized Cu surfaces diminishes with increasing carbon chain length, their steric hindrance increases. EtOH was identified as the optimal pretreatment agent, yielding an exceptional selectivity exceeding 99.9% on SiO2/Cu patterned surface. Moreover, the alcohol-mediated AS-ALD process is successfully extended to other oxide systems with precursors bearing analogous ligands, demonstrating the generality of the proposed strategy. This work provides a versatile methodology for modulating surface reductive capability and steric hindrance to achieve high-selectivity AS-ALD.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"158 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152041","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

Accurately Probing [Fe(CN)6] Defects in Prussian Blue Analogues 普鲁士蓝类似物中[Fe(CN)6]缺陷的精确探测

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-12 DOI: 10.1021/acs.chemmater.6c02095

Romain Wernert,Long H. B. Nguyen,Mathieu Duttine,François Fauth,Lorenzo Stievano,Dany Carlier,Laurence Croguennec

{"title":"Accurately Probing [Fe(CN)6] Defects in Prussian Blue Analogues","authors":"Romain Wernert,Long H. B. Nguyen,Mathieu Duttine,François Fauth,Lorenzo Stievano,Dany Carlier,Laurence Croguennec","doi":"10.1021/acs.chemmater.6c02095","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02095","url":null,"abstract":"Prussian blue analogues AxM[Fe(CN)6]1–y·zH2O (A = Na, K, M = Fe, Mn) possess a rich crystal chemistry that allows their use as insertion materials for batteries, water treatment, and smart windows, among others, applications. Despite being simple in appearance, their synthesis is complex and often results in defective, nonstoichiometric materials. These defects can be of neutral charge, such as interstitial water molecules, or charged, such as A+ vacancies or [Fe(CN)6]n− vacancies, whose presence implies charge balance by the remaining transition metal centers. In this work, a compound close to the Berlin green Fe[Fe(CN)6] nominal composition was synthesized, and its crystal structure, electrochemical properties, and electronic structure were investigated. Although usual characterization methods such as X-ray diffraction, X-ray absorption spectroscopy, and 57Fe Mössbauer spectroscopy agree well with the formation of Fe[Fe(CN)6], the material can only be intercalated to Na1.4Fe[Fe(CN)6]. This lack of capacity was hypothesized to arise from “hidden” [Fe(CN)6] vacancies. The charge balance associated with these vacancies implies partial reduction of the low-spin Fe, as confirmed by low-temperature 57Fe Mössbauer spectroscopy and further high-angular-resolution diffraction experiments. This study suggests that numerous materials previously described as “Berlin green” in the literature might actually be substantially hexacyanoferrate defective.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152043","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

Concerted Ge–H/Se–Se Bond Reorganization Enables Surface Selenylation of Germanium Quantum Dots 协同Ge-H / Se-Se键重组实现锗量子点的表面硒化

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-12 DOI: 10.1021/acs.chemmater.6c02278

Xuebiao Deng,Jintao Meng,Yilan Zhang,Meiqi Lin,Jingpeng Li,Kaoxian Mo,Xiaoning Cheng,Zhenyu Yang

引用次数: 0

Orbital Coupling Engineering through P-Block Metal Doping in NiFe Layered Double Hydroxides for Enhanced Anion-Exchange Membrane Water Electrolysis 利用p -嵌段金属掺杂NiFe层状双氢氧化物的轨道耦合工程增强阴离子交换膜电解

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-11 DOI: 10.1021/acs.chemmater.6c01912

Sreenivasan Nagappan,Harpriya Minhas,Suprobhat Singha Roy,Seiji Yamazoe,Aditi De,Prasita Mazumder,Soichi Kikkawa,Asha K Satheesan,Hariharan N Dhandapani,Arun Karmakar,Biswarup Pathak,Subrata Kundu

{"title":"Orbital Coupling Engineering through P-Block Metal Doping in NiFe Layered Double Hydroxides for Enhanced Anion-Exchange Membrane Water Electrolysis","authors":"Sreenivasan Nagappan,Harpriya Minhas,Suprobhat Singha Roy,Seiji Yamazoe,Aditi De,Prasita Mazumder,Soichi Kikkawa,Asha K Satheesan,Hariharan N Dhandapani,Arun Karmakar,Biswarup Pathak,Subrata Kundu","doi":"10.1021/acs.chemmater.6c01912","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01912","url":null,"abstract":"The oxygen evolution reaction (OER) remains a major kinetic bottleneck in anodic water splitting because of sluggish adsorption and desorption kinetics of O-containing intermediates. Optimizing the adsorption strength of various O-containing intermediates in accordance with the Sabatier principle involves the precise tuning of the active-site electronic structure. Herein, we explore a p-block metal-assisted synergism regulation strategy in NiFe layered double hydroxides (LDHs) by introducing group-13 elements (Al, Ga, In) as dopants. Among various doped LDHs, In-doped NiFe-LDH shows the highest OER activity by demanding an overpotential value of 298 mV at 10 mA/cm2 along with enhanced intrinsic turnover frequency and long-term stability. X-ray absorption spectroscopy (XAS) reveals that In3+ preferentially occupies the Fe coordination sites, while valence-band X-ray photoelectron spectroscopy (VB-XPS) confirms enhanced electronic coupling in the Ni–O–In framework. Density functional theory (DFT) additionally suggests that the In 5p orbitals strongly hybridize with the O 2p and Ni 3d states, establishing a Ni3d-O2p-In5p electronic interaction that regulates the Ni electronic structure and optimizes the adsorption energies of O-containing intermediates. The resulting d-p-p orbital hybridization offers an efficient pathway for charge delocalization and strengthens the M–O covalency, thereby accelerating the OER kinetics. This study elucidates the structure–activity relationship and identifies p-block metal-induced orbital hybridization as an effective strategy for developing high-performance oxygen evolution electrocatalysts, offering an alternative to conventional transition-metal modification approaches.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"53 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152038","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

Synergy of Solid-State NMR and Dielectric Spectroscopy Reveals Synchronized Multi-Rotor Dynamics in Crystalline Supramolecular Gyroscopes 固态核磁共振和介电光谱的协同作用揭示了晶体超分子陀螺仪的同步多转子动力学

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-11 DOI: 10.1021/acs.chemmater.6c01722

Qing Wang,Wei-Yu Hu,Wang Li,Zi-Yi Du,Wei-Xiong Zhang,Haiming Liu

{"title":"Synergy of Solid-State NMR and Dielectric Spectroscopy Reveals Synchronized Multi-Rotor Dynamics in Crystalline Supramolecular Gyroscopes","authors":"Qing Wang,Wei-Yu Hu,Wang Li,Zi-Yi Du,Wei-Xiong Zhang,Haiming Liu","doi":"10.1021/acs.chemmater.6c01722","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01722","url":null,"abstract":"Understanding the correlated dynamics of multiple molecular rotators in crystalline supramolecular assemblies is essential for designing functional molecular machines, yet deconvoluting the motions of distinct components remains inherently challenging due to the limitations of individual techniques. Here, we report a synergistic approach that combines solid-state Nuclear Magnetic Resonance (SSNMR) and dielectric spectroscopy to quantitatively resolve multirotor dynamics in a family of isostructural supramolecular gyroscopic complex architectures composed of alkyl ammonium, crown ether, and metal halide hydrate. SSNMR unambiguously reveals both the tert-butylammonium cation and the 18-crown-6 macrocycle as independent rotators─a distinction often ambiguous in such systems. Crucially, by correlating SSNMR-derived dynamics of the crown ether with dielectric relaxation of the coordinated water molecule, we uncover their synchronized rotation across a wide temperature range, mediated by charge-assisted hydrogen bonding. These findings reveal a cooperative multirotor gyroscopic model featuring synchronous rotation of an integrated coaxial crown ether–water–ammonium trio-rotator, accompanied by correlated alkyl reorientation. This synergy validates the dielectric relaxation principle in a complex, multirotor crystalline environment where unambiguous peak assignment has been a longstanding challenge. This work establishes a generalizable methodology for dissecting complex, multicomponent dynamics in crystalline materials, directly bridging molecular-scale motion to macroscopic dielectric response.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152040","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

Unravelingthe Mystery of Near-Infrared Emission inan Antimony Halide Dimer Driven by the Jahn–Teller Effect 解开由扬-泰勒效应驱动的卤化锑二聚体近红外发射之谜

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-10 DOI: 10.1021/acs.chemmater.6c02476

Jia Jiang,Weihao Wang,Yage Ji,Yulin Zhang,Zhuozi Lin,Yalin An,Yuhui Zheng,Qianming Wang

{"title":"Unraveling\u0000the Mystery of Near-Infrared Emission in\u0000an Antimony Halide Dimer Driven by the Jahn–Teller Effect","authors":"Jia Jiang,Weihao Wang,Yage Ji,Yulin Zhang,Zhuozi Lin,Yalin An,Yuhui Zheng,Qianming Wang","doi":"10.1021/acs.chemmater.6c02476","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02476","url":null,"abstract":"Abstract Most zero-dimensional hybrid metal halides enable emission in the first near-infrared (NIR-I) region (650–950 nm), and the shorter wavelengths result in poor photon penetration depth. Here, we report the observation of an NIR-II emission signal (band gap = 1.13 eV) from a (BTBAC)2Sb2Cl8 single crystal at room temperature. Although a variety of mechanisms are involved in the explanation of such a broad band with a large Stokes shift, the exploration of the structural origin of the NIR optical activity remains challenging due to misconceptions about excitons and experimental limitations. A strategy that spatially confines 5s2 ions within edge-shared [Sb2Cl8]2– units with controlled lattice distortion is proposed to cause a Jahn–Teller effect (JTE) during the interconfiguration transition (3P1 → 1S0). A family of hybrid metal halides doped with Bi3+,In3+ or Bi3+/In3+ demonstrates that the fine interplay between the Jahn–Teller effect and spin–orbit coupling (SOC) takes into full consideration orbital degeneracy and electron flipping, thus boosting the photoluminescence quantum yield to 12%. TD-DFT calculations visualize the symmetry of the two lattices within a dimeric structure varying with specific modes, and the rational assignment of the energy gap (ground state: 3.69 eV; excited state: 1.22 eV) between 1S0 and 3P1 is highly consistent with the experimental findings (λex = 330 nm; λem = 1100 nm). Leveraging the (BTBAC)2Sb2Cl8 sample, electroluminescence pumped by a UV-LED chip yields a highly efficient NIR-II emission, and the phosphor displays diverse functions in night vision and anticounterfeiting.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"19 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151055","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

Practical Considerations for Operando 7Li Nuclear Magnetic Resonance in Coin and Pouch Cells 硬币和袋状细胞中Operando 7Li核磁共振的实际考虑

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-10 DOI: 10.1021/acs.chemmater.6c01590

Asya Svirinovsky-Arbeli,Yongbeom Kwon,Diana Oh,Kaitlin Rae M. Corpus,Pascal Scholzen,Piotr Lepucki,Oliver Pecher,Lauren E. Marbella

{"title":"Practical Considerations for\u0000 Operando\u0000 7Li Nuclear Magnetic Resonance in Coin and Pouch Cells","authors":"Asya Svirinovsky-Arbeli,Yongbeom Kwon,Diana Oh,Kaitlin Rae M. Corpus,Pascal Scholzen,Piotr Lepucki,Oliver Pecher,Lauren E. Marbella","doi":"10.1021/acs.chemmater.6c01590","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01590","url":null,"abstract":"Abstract Operando nuclear magnetic resonance (NMR) spectroscopy provides unique insight into chemical changes in batteries during use but has largely been limited to custom plastic cells. Unfortunately, the metal casings that house commercial batteries distort and shield radiofrequency (RF) fields required for excitation and detection in NMR. Here, we use operando7Li NMR spectroscopy to study metal-encased batteries in both coin and pouch cell formats without modifying the cell or casing. We benchmark NMR spectra obtained from stainless-steel coin cells and aluminum-laminate pouch cells to plastic coin cells and show that casing composition, auxiliary hardware, and sample placement strongly influence observed shift, signal intensity, and line shape due to bulk magnetic susceptibility effects and RF attenuation upon interacting with cell parts. These effects are most severe in stainless-steel coin cells (and in particular 304-grade stainless steel) but can be mitigated through the use of Al spacers while retaining the stainless-steel caps and springs. In light of these considerations, we leverage operando7Li NMR to track lithium plating/stripping and monitor the accumulation of electrochemically inactive “dead” lithium (Li0) during galvanostatic cycling in coin and pouch cells. In pouch cells, the lean electrolyte volume allows us to resolve changes in the 7Li electrolyte signal during formation that are consistent with electrolyte redistribution and wetting. Taken together, these results demonstrate how to alter cell susceptibility to improve NMR signals during operando measurements in commercially relevant form factors while also establishing the cell design constraints that limit quantitative interpretation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"9 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151054","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

Diffusion-LimitedSolid-State Synthesis Selectivityin the Presence of Oxidation/Reduction Processes 氧化/还原过程存在下的扩散限制固态合成选择性

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-09 DOI: 10.1021/acs.chemmater.6c01610

Vir Karan,Kristin A. Persson

{"title":"Diffusion-Limited\u0000Solid-State Synthesis Selectivity\u0000in the Presence of Oxidation/Reduction Processes","authors":"Vir Karan,Kristin A. Persson","doi":"10.1021/acs.chemmater.6c01610","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01610","url":null,"abstract":"Abstract Solid-state synthesis outcomes arise from an interplay between thermodynamics and kinetics, with their relative importance governed by external control parameters such as temperature profiles and precursor selection. A recently introduced framework, combining first-principles thermodynamics with machine-learning-enabled simulations of correlated ion transport, successfully captured this interplay in the Ba–Ti–O system by linking phase selectivity to ion mobility within “liquid-like”, amorphous interphases. Notably, in systems where valence states can change during synthesis, ion dynamics are strongly coupled to oxidation state. Here, we extend the framework to such mixed-valence systems and demonstrate its predictive power for the synthesis of ternary metal ferrites in the Ba–Fe–O and Y–Fe–O systems, benchmarked against in situ XRD experiments. Similar to the Ba–Ti–O system, we hypothesize that the rate-limiting transport of ionic species governing polymorph growth occurs through a “liquid-like,” noncrystalline interphase. To capture this behavior, we employ a charge-informed machine-learning potential (CHGNet) that enables modeling of correlated, redox-dependent transport. We find that the framework accurately predicts the sequence of phase formation and the time evolution of phase distributions in powder synthesis reactions, in agreement with experimental reports. These results show that diffusion-limited phase selectivity can be treated on a unified footing across mixed-valence oxides, further clearing a pathway toward rational, in silico synthesis design that simultaneously accounts for thermodynamic and kinetic factors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151514","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

Light-Induced Self-Healing Behavior in PhotosalientCoordination Polymer 光显着配位聚合物的光诱导自愈行为

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-09 DOI: 10.1021/acs.chemmater.6c01622

Uma Kurakula,Sourav Datta,Basudeb Dutta,Smita Singh,Sesha Vempati,Mohammad Hedayetullah Mir,Raghavender Medishetty

{"title":"Light-Induced Self-Healing Behavior in Photosalient\u0000Coordination Polymer","authors":"Uma Kurakula,Sourav Datta,Basudeb Dutta,Smita Singh,Sesha Vempati,Mohammad Hedayetullah Mir,Raghavender Medishetty","doi":"10.1021/acs.chemmater.6c01622","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01622","url":null,"abstract":"Abstract Achieving self-healing in the photosalient (PS) crystals without compromising structural integrity is a challenge. So far, self-healing and photomechanical behaviors have predominantly been reported as independent phenomena. Systems that concurrently exhibit both properties under a single stimulus remain uncommon. Here, we report the integration of the photomechanical property with a self-healing behavior by embedding dynamic covalent disulfide (S–S) linkages into a photoreactive coordination polymer (CP). Using 2-mercaptobenzoic acid, which undergoes in situ oxidation to form S–S bonds during crystallization, we obtained two-dimensional (2D) CP. The crystal undergoes cracking followed by a pronounced PS motion under UV irradiation. Continued irradiation induces up to 95% volumetric self-healing, as confirmed by atomic force microscopy, and acts as a self-healing optical window by restoring optical transparency and single-crystal integrity, as verified by multimodal microscopic techniques and single-crystal X-ray diffraction (SXRD). Comprehensive analysis using SXRD and spectroscopy collectively disentangles both mechanisms, viz solid-state [2 + 2] cycloaddition, which is responsible for cracking, PS behavior, and dynamic covalent chemistry (DCC) (S–S) that enables subsequent self-healing. This work demonstrates a distinctive combination of cracking, PS, and self-healing behavior in a CP enabled by the synergistic interplay of light-induced irreversible [2 + 2] photocycloaddition and dynamic disulfide bond linkage within a single crystal, in addition to a 2D CP to 3D CP transformation mediated by an “SC-crack-heal-SC” (Single Crystal → Cracked Crystal → Crystal Healing → Healed Single Crystal) mechanism. This approach paves the way for advancements in soft robotics, adaptive optics, and resilient next-generation functional materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"54 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151058","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