Chemistry of Materials最新文献

{"title":"Structure–Activity Relationship Studies of Glycosaminoglycan Mimetic Macrocycles Against Herpes","authors":"Sujeet Pawar,&nbsp;Hien Thi Tran,&nbsp;Melis Özkan,&nbsp;Deepika Sardana,&nbsp;Cynthia Paloma Aigroz,&nbsp;Paulo Jacob Silva,&nbsp;Anita Zucchi and Francesco Stellacci*,&nbsp;","doi":"10.1021/acs.chemmater.4c0201610.1021/acs.chemmater.4c02016","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02016https://doi.org/10.1021/acs.chemmater.4c02016","url":null,"abstract":"<p >The herpes simplex virus (HSV) is associated with serious conditions, such as encephalitis and blindness, and its infection is closely linked to significant vascular complications and coagulation issues, particularly in individuals with compromised immune systems. Current antiviral treatments often fall short of effectively eliminating viral shedding and face resistance and are not entirely effective in managing coagulation. HSV recognition of heparan sulfate on cell walls for entry is well-established. A possible strategy to effectively address HSV infections involves developing agents with both antiviral and anticoagulant properties. Recently, multivalent entry inhibitors (MEI) against HSV have been developed. Among the most promising candidates is an MEI that uses a β-cyclodextrin as a scaffold to hold six elongated 11-methylene long alkyl (C11) chains, each terminated with sodium sulfonates. This MEI exhibits irreversible inhibition of viral infectivity (virucidal mechanism) with some good results in vivo. The role of the cyclodextrin core is simply to hold the arms together. Here, we present an investigation of other potential core candidates, and we compare their structure–activity for viral inhibition. We find that all cores functionalized with C12 chains terminated with either sulfate or sulfonate are effective in inhibiting both HSV1 and HSV2, all with a virucidal mechanism. We find significant differences in the half inhibitory concentration (IC₅₀), the best core being <i>p</i>-<i>tert</i>-butylcalix[4]arene when functionalized with C12 sodium sulfonate terminated arms. This core showed an IC₅₀ of 8.3 μM against HSV-1 and 10.6 μM against HSV-2 a drastic improvement over the β-cyclodextrin. We investigated the anticoagulant property of our lead compound by inhibiting factor Xa, a key enzyme in coagulation cascade pathways, and found similar inhibition to that of the FDA-approved drug fondaparinux. Thus, our compound presents a nonsaccharide-based prophylactic dual inhibitor against HSV infections.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2087–2096 2087–2096"},"PeriodicalIF":7.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorine-Induced Anomalous Optical Stability and Pressure-Enhanced Emission Property of 0D Lead Perovskite Derivatives","authors":"Congcong Chen,&nbsp;Yifan Zhang,&nbsp;Huan Liu,&nbsp;Xuanyu Zhang,&nbsp;Zhongshiqi Luo,&nbsp;Jiawei Lin,&nbsp;Yuhong Mao,&nbsp;Rui Chen,&nbsp;Songhao Guo*,&nbsp;Xujie Lü and Lingling Mao*,&nbsp;","doi":"10.1021/acs.chemmater.5c0011210.1021/acs.chemmater.5c00112","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00112https://doi.org/10.1021/acs.chemmater.5c00112","url":null,"abstract":"<p >Low-dimensional metal halides, especially zero-dimensional (0D) compounds, are important derivative members of the halide perovskite family primarily due to their highly emissive properties. Here, we report two highly luminescent 0D lead bromides, (BPP)₂PbBr₄ and (BPPF)₂PbBr₄·2H₂O, abbreviated as BPP-0D and BPPF-0D (BPP = benzyltriphenylphosphonium, BPPF = (4-fluorobenzyl)triphenylphosphonium). Both compounds share mutual seesaw inorganic units [PbBr₄]^2– separated by bulky organic cations. BPP-0D and BPPF-0D emit yellow and green lights, respectively, with photoluminescence (PL) quantum yields (PLQYs) of ∼15 and ∼55% at ambient conditions. Both compounds show excellent environmental stability and practical applications in light-emitting diodes. Upon compression, BPP-0D experiences a rapid decrease in PL intensity, accompanied by an obvious change in its emissive color from yellow to blue. In contrast, BPPF-0D demonstrates excellent optical stability, retaining its green emission, while the PL increases by ∼1.7 times at 0.8 GPa and the PLQY increases to 93%. For BPPF-0D, the presence of an extra highly electronegative fluoride group adds many more noncovalent interactions, such as C–H···F hydrogen bond and F···F interactions. These interactions strengthen the structural and optical stabilities of BPPF-0D, maintaining its emission peak position with elevated pressure. The straightforward comparison between two similar compounds and their optical properties under pressure modulation underscores the importance of engineering organic cations to control and optimize their properties.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2314–2324 2314–2324"},"PeriodicalIF":7.2,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678502","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":"Redox-Responsive Polyprodrugs: Recent Innovations in Reduction- and Oxidation-Responsive Drug Delivery Systems","authors":"Arjaree Jobdeedamrong,&nbsp; and ,&nbsp;Daniel Crespy*,&nbsp;","doi":"10.1021/acs.chemmater.4c0318110.1021/acs.chemmater.4c03181","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03181https://doi.org/10.1021/acs.chemmater.4c03181","url":null,"abstract":"<p >Redox-responsive polyprodrugs are innovative drug delivery systems that exploit the fact that diseased tissues display distinct microenvironments. These systems feature polymeric backbones or side chains displaying redox-sensitive bonds, enabling a targeted, site-specific drug release in response to oxidation or reduction. This approach minimizes off-target effects and enhances the therapeutic outcomes. Reduction-responsive polyprodrugs contain cleavable bonds, such as disulfide linkages and Pt–ligand bonds in platinum complexes, which can be cleaved through reduction reactions. Disulfide bonds are cleaved in the presence of increased concentrations of intracellular glutathione, hence specifically triggering drug release within tumor cells. The reduction of Pt(IV) to Pt(II) converts inactive platinum prodrugs into active chemotherapeutic agents, enabling targeted cancer treatment. Oxidation-responsive bonds, including boronate esters, thioketal, oxalate, and thiolacetal bonds, are cleaved by reactive oxygen species (ROS) such as hydrogen peroxide, releasing drugs in ROS-rich tumor microenvironments. Furthermore, combining both reduction- and oxidation-responsive bonds in a single polyprodrug enhances selectivity and efficacy, allowing for synchronized drug release in complex tumor environments characterized by both oxidative stress and high glutathione levels. Additionally, redox-responsive polyprodrugs can be engineered to lead to greater stability, controlled degradation, and multifunctional responsiveness, making them versatile tools in precision medicine. Beyond cancer, these polyprodrugs have potential applications in treating inflammatory diseases and creating smart materials for industrial use, such as anticorrosion coatings.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2073–2086 2073–2086"},"PeriodicalIF":7.2,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678490","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":"Redox-Responsive Polyprodrugs: Recent Innovations in Reduction- and Oxidation-Responsive Drug Delivery Systems","authors":"Arjaree Jobdeedamrong, Daniel Crespy","doi":"10.1021/acs.chemmater.4c03181","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03181","url":null,"abstract":"Redox-responsive polyprodrugs are innovative drug delivery systems that exploit the fact that diseased tissues display distinct microenvironments. These systems feature polymeric backbones or side chains displaying redox-sensitive bonds, enabling a targeted, site-specific drug release in response to oxidation or reduction. This approach minimizes off-target effects and enhances the therapeutic outcomes. Reduction-responsive polyprodrugs contain cleavable bonds, such as disulfide linkages and Pt–ligand bonds in platinum complexes, which can be cleaved through reduction reactions. Disulfide bonds are cleaved in the presence of increased concentrations of intracellular glutathione, hence specifically triggering drug release within tumor cells. The reduction of Pt(IV) to Pt(II) converts inactive platinum prodrugs into active chemotherapeutic agents, enabling targeted cancer treatment. Oxidation-responsive bonds, including boronate esters, thioketal, oxalate, and thiolacetal bonds, are cleaved by reactive oxygen species (ROS) such as hydrogen peroxide, releasing drugs in ROS-rich tumor microenvironments. Furthermore, combining both reduction- and oxidation-responsive bonds in a single polyprodrug enhances selectivity and efficacy, allowing for synchronized drug release in complex tumor environments characterized by both oxidative stress and high glutathione levels. Additionally, redox-responsive polyprodrugs can be engineered to lead to greater stability, controlled degradation, and multifunctional responsiveness, making them versatile tools in precision medicine. Beyond cancer, these polyprodrugs have potential applications in treating inflammatory diseases and creating smart materials for industrial use, such as anticorrosion coatings.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627572","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":"Circularly Polarized Light-Regulable Crystal–Liquid Phase Transition of Self-Assembled Macroscopic Chiral Twisted Ribbons","authors":"Xin Dong,&nbsp;Yixuan Jiang,&nbsp;Yanyi He,&nbsp;Jingsong Feng,&nbsp;Xiao-Qi Yu and Shanshan Yu*,&nbsp;","doi":"10.1021/acs.chemmater.5c0047810.1021/acs.chemmater.5c00478","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00478https://doi.org/10.1021/acs.chemmater.5c00478","url":null,"abstract":"<p >Chirality is a fundamental property of nature, observed at the subatomic, molecular, supramolecular, and macroscopic levels. Circularly polarized light (CPL) has attracted extensive attention as an effective tool for regulating and inducing chirality on various scales. Herein, we report the formation of micron-scale twisted ribbons from homochiral molecular H₈-BAz through self-assembly driven by solvophobic interactions. The chiral information in H₈-BAz is effectively transferred and amplified in the supramolecular structure and finally appears as macroscopic homochiral twisted ribbons that match the chirality of the monomers. The ribbons undergo a photoinduced crystal-to-liquid transition (PCLT) when exposed to 365 nm light due to the isomerization of the azobenzene structure. Additionally, the PCLT behavior of chiral ribbons is regulated by CPL: When irradiated with homochiral right-handed CPL (RCP), the ribbon with a <i>P</i>-helix formed by (<i>R</i>)-H₈-BAz undergoes a faster phase transition. The <i>M</i>-helix ribbon undergoes a faster phase transition with left-handed CPL (LCP). The average time difference for the phase transition reaches 1.5 times. Our results demonstrate a simple method for creating macroscopic chiral structures and the impact of chiral light sources on their phase transition process.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2379–2388 2379–2388"},"PeriodicalIF":7.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678666","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":"Coordination of Mg(II) Enhancing Photoinduced Oxidase-Like Activity of Carbon Dots for Efficient Degradation of Organic Dyes","authors":"Jinyu Shi,&nbsp;Jing Li,&nbsp;Xuemin Li,&nbsp;Yu Zhang,&nbsp;Jiao Hu,&nbsp;Yu Ning,&nbsp;Chuan-Hua Zhou*,&nbsp;Zhining Xia* and Cui Liu*,&nbsp;","doi":"10.1021/acs.chemmater.5c0003710.1021/acs.chemmater.5c00037","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00037https://doi.org/10.1021/acs.chemmater.5c00037","url":null,"abstract":"<p >Water pollution caused by organic dyes not only seriously damages the ecological environment but also poses a great threat to human health. Herein, the doping of Mg(II) enhancing the photoinduced oxidase-like activity of carbon dots (CDs) in a wide pH range from 2.3 to 8.2 is reported. The Mg-CDs catalyze the generation of superoxide anions (O₂^•–) and singlet oxygen (¹O₂) from dissolved oxygen under light irradiation. Compared to CDs without Mg(II) doping, Mg-CDs exhibit much higher photoinduced oxidase-like activity (more than 250%) because the coordination of Mg(II) facilitates the content ratio of enol to ketone, enhancing the rigidity of the π-system and boosting the electron transition within CDs. A universal strategy for degrading organic dyes, including azo, triphenylmethane alkaline, and alkaline azo dyes, is constructed based on the remarkable photoinduced oxidase-like performance of Mg-CDs. The degradation rates of methyl orange, crystal violet, and rhodamine B are 92.2%, 96.5%, and 98.5%, respectively. Our findings provide a strategy to design desirable photoinduced nanozymes for water pollution control and demonstrate great potential of metal-doped CDs in photocatalysis.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2290–2301 2290–2301"},"PeriodicalIF":7.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678807","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":"Coordination of Mg(II) Enhancing Photoinduced Oxidase-Like Activity of Carbon Dots for Efficient Degradation of Organic Dyes","authors":"Jinyu Shi, Jing Li, Xuemin Li, Yu Zhang, Jiao Hu, Yu Ning, Chuan-Hua Zhou, Zhining Xia, Cui Liu","doi":"10.1021/acs.chemmater.5c00037","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00037","url":null,"abstract":"Water pollution caused by organic dyes not only seriously damages the ecological environment but also poses a great threat to human health. Herein, the doping of Mg(II) enhancing the photoinduced oxidase-like activity of carbon dots (CDs) in a wide pH range from 2.3 to 8.2 is reported. The Mg-CDs catalyze the generation of superoxide anions (O₂^•–) and singlet oxygen (¹O₂) from dissolved oxygen under light irradiation. Compared to CDs without Mg(II) doping, Mg-CDs exhibit much higher photoinduced oxidase-like activity (more than 250%) because the coordination of Mg(II) facilitates the content ratio of enol to ketone, enhancing the rigidity of the π-system and boosting the electron transition within CDs. A universal strategy for degrading organic dyes, including azo, triphenylmethane alkaline, and alkaline azo dyes, is constructed based on the remarkable photoinduced oxidase-like performance of Mg-CDs. The degradation rates of methyl orange, crystal violet, and rhodamine B are 92.2%, 96.5%, and 98.5%, respectively. Our findings provide a strategy to design desirable photoinduced nanozymes for water pollution control and demonstrate great potential of metal-doped CDs in photocatalysis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618970","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":"Understanding the Beneficial Role of Transition-Metal Layer Na+ Substitution on the Structure and Electrochemical Properties of the P2-Layered Cathode Na2+xNi2–x/2TeO6","authors":"Nicholas S. Grundish, Graeme Henkelman, John B. Goodenough, Claude Delmas, Dany Carlier, Ieuan D. Seymour","doi":"10.1021/acs.chemmater.4c02798","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02798","url":null,"abstract":"Layered Na_<i>x</i>MO₂ sodium oxide positive electrode materials have experienced renewed interest owing to the current commercial attention on sodium-ion batteries. Although there are many attractive qualities of these materials, they suffer from serious shortcomings owing to Na⁺ ordering and transition-metal layer gliding that cause a plethora of voltage plateaus during cycling. The P2-layered Na_2+<i>x</i>Ni_{2–<i>x</i>/2}TeO₆ (0 ≤ <i>x</i> ≤ 0.5) system provides a framework for investigating the effect of dual Na⁺ substitution into the sodium layer and the transition-metal layer of the structure and its effects on the electrochemical properties of the materials. A careful investigation into the synthesis and properties of these materials reveals that the sodium content used during material preparation has a drastic effect on the composition and electrochemical profile of these materials. The sodium substitution disrupts ordering within the transition-metal layer, thereby disrupting Na⁺ ordering in the adjacent sodium layers. Beyond a critical sodium concentration, the layer stacking shifts, and all voltage plateaus of the P2-Na₂Ni₂TeO₆ material are no longer observed at 4.4 V versus Na⁺/Na. These results also question the common belief that additional sodium precursor is required when preparing layered sodium oxide cathodes, providing new guidelines for material synthesis and characterization.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618941","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":"Circularly Polarized Light-Regulable Crystal–Liquid Phase Transition of Self-Assembled Macroscopic Chiral Twisted Ribbons","authors":"Xin Dong, Yixuan Jiang, Yanyi He, Jingsong Feng, Xiao-Qi Yu, Shanshan Yu","doi":"10.1021/acs.chemmater.5c00478","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00478","url":null,"abstract":"Chirality is a fundamental property of nature, observed at the subatomic, molecular, supramolecular, and macroscopic levels. Circularly polarized light (CPL) has attracted extensive attention as an effective tool for regulating and inducing chirality on various scales. Herein, we report the formation of micron-scale twisted ribbons from homochiral molecular H₈-BAz through self-assembly driven by solvophobic interactions. The chiral information in H₈-BAz is effectively transferred and amplified in the supramolecular structure and finally appears as macroscopic homochiral twisted ribbons that match the chirality of the monomers. The ribbons undergo a photoinduced crystal-to-liquid transition (PCLT) when exposed to 365 nm light due to the isomerization of the azobenzene structure. Additionally, the PCLT behavior of chiral ribbons is regulated by CPL: When irradiated with homochiral right-handed CPL (RCP), the ribbon with a <i>P</i>-helix formed by (<i>R</i>)-H₈-BAz undergoes a faster phase transition. The <i>M</i>-helix ribbon undergoes a faster phase transition with left-handed CPL (LCP). The average time difference for the phase transition reaches 1.5 times. Our results demonstrate a simple method for creating macroscopic chiral structures and the impact of chiral light sources on their phase transition process.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618943","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":"Colossal Thermal Expansion in Ca-Substituted PbCrO3","authors":"Qiumin Liu, Takumi Nishikubo, Kazuki Takahashi, Seiho Higashi, Yusuke Shibata, Jun Miyake, Kano Hatayama, Yuki Sakai, Teppei Nagase, Koki Matsushima, Runze Yu, Takafumi Yamamoto, Masaki Azuma","doi":"10.1021/acs.chemmater.5c00090","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00090","url":null,"abstract":"Colossal thermal expansion, 11.9% volume expansion on heating, was observed in Pb_0.7Ca_0.3CrO₃. The parent compound, PbCrO₃, had been known to have a characteristic Pb²⁺_0.5Pb⁴⁺_0.5Cr³⁺O₃ charge distribution with a glassy distribution of Pb²⁺ and Pb⁴⁺ in ambient conditions and undergoes a charge transfer transition to the Pb²⁺Cr⁴⁺O₃ high-pressure phase at 2.5 GPa. It decomposes at 720 K without such a transition when heated at ambient pressure. Our in-situ synchrotron X-ray diffraction study revealed a temperature-induced phase transition from Pb²⁺Cr⁴⁺O₃ to Pb_²⁺0.5Pb⁴⁺_0.5Cr³⁺O₃ at moderate pressures between 2 and 3.5 GPa. Ca substitution for Pb shifted the phase boundary in the pressure–temperature space, and essentially the same charge transfer transition was caused by heating at ambient pressure. A remarkable volume change of 11.9% occurred, corresponding to a colossal linear thermal expansion coefficient of 550 ppm/K─an unprecedented value in oxide ceramics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599622","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}