Chemistry of Materials最新文献

{"title":"Synthesis, Characterization, and Thermolysis Studies of Binary Malondialdehydate Complexes of Copper(II) and Palladium(II)","authors":"Nathan D. Edmonsond, Vincent J. Flores, Gregory S. Girolami","doi":"10.1021/acs.chemmater.5c00568","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00568","url":null,"abstract":"An improved preparation of the malondialdehydate (mda) salt Na(mda)(H₂O) is reported; also described are preparations of copper(II) and palladium(II) complexes of mda and its 2-phenylmalondialdehydate (2-Ph-mda) analog. Crystal structures of Na(mda)(H₂O), Cu(mda)₂, Cu(2-Ph-mda)₂, Pd(mda)₂, and Pd(2-Ph-mda)₂ are described, along with nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) data. Cu(mda)₂ and Pd(mda)₂ deposit metallic thin films at 130 °C under chemical vapor deposition (CVD) conditions. Mechanistic studies show that Cu(mda)₂ transforms to copper metal by means of a ligand fragmentation pathway that involves carbon–carbon bond scission reactions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"31 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122663","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":"Glass-Ceramic Lithium Thiophosphate Electrolytes with Enhanced Conductivity and (Chemo)mechanical Properties for All-Solid-State Batteries","authors":"Jingui Yang, Mareen Schaller, Gennady Cherkashinin, Ruizhuo Zhang, Sylvio Indris, Daniel Alves Dalla Corte, Aleksandr Kondrakov, Torsten Brezesinski, Florian Strauss","doi":"10.1021/acs.chemmater.5c00234","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00234","url":null,"abstract":"Solid-state batteries (SSBs) based on inorganic solid electrolytes (SEs) possibly offer enhanced energy and power densities, along with increased safety, compared to state-of-the-art rechargeable batteries using liquid organic electrolytes. However, the stiffness and brittle nature of inorganic SEs can complicate cell fabrication and lead to the (chemo)mechanical failure of SSBs during operation. In the past, the design of SEs has mainly focused on optimizing the ionic conductivity and (electro)chemical stability. However, to mitigate detrimental (chemo)mechanical degradation in SSBs, due to electrode volume and morphology changes upon charge and discharge, the mechanical properties of SEs also need to be considered in their development. In this regard, glass-ceramic SEs offer a reduced hardness but often suffer from rather low ionic conductivities. Herein we systematically investigate the effect of LiI additive and annealing temperature on phase composition and charge-transport properties of a series of SEs with the general composition of 4.25Li₂S–0.75P₂S₅–1.5SiS₂–<i>x</i>LiI (0 ≤ <i>x</i> ≤ 2). We demonstrate that the glass-ceramic material (LPSI-GC) with <i>x</i>(LiI) = 1.25 achieves a high room-temperature ionic conductivity of 4.38 mS cm^–1 and further exhibits favorable mechanical properties owing to the combination of crystalline <i>t</i>-Li_10.5P_1.5Si_1.5S₁₂ and I-rich amorphous phases. When implemented in SSBs together with a layered Ni-rich oxide cathode material, the LPSI-GC SE enables stable cycling for over 100 cycles, although (electro)chemical decomposition, detected by X-ray photoelectron spectroscopy, is evident. Collectively, our results demonstrate that glass-ceramic SEs allow for simultaneous optimization of the ionic conductivity and mechanical properties, thus enabling long-term SSB operation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"59 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Copper-Rich Multinary Iodido Bismuthate with Cationic Ligands and Broad Red Emission","authors":"Jakob Möbs, Philip Klement, Lukas Gümbel, Paula Epure, Florian Weigend, Sangam Chatterjee, Johanna Heine","doi":"10.1021/acs.chemmater.5c00306","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00306","url":null,"abstract":"Lead halide perovskites and related hybrid metal halides exhibit exceptional semiconductor properties, enabling diverse applications in photovoltaics, solid-state lighting, and photocatalysis. Multinary halido metalates, combining multiple metals, offer unique opportunities to tune the optical and electronic properties of these materials for specific applications. Here, we present the synthesis and characterization of (Hpiz)₄BiCu₄I₁₁·2MeCN (piz = piperazine), the most copper-rich molecular iodido bismuthate reported to date, featuring a Cu/Bi ratio of 4:1. It extends the “all-in-one” design concept of halido cuprates with cationic ligands to multinary systems and exhibits a low optical band gap of 1.82 eV (681 nm) and broad red photoluminescence centered at 1.69 eV (735 nm), making it a promising candidate for light-harvesting and near-infrared emission applications. Quantum chemical analyses attribute the reduced band gap to strong electronic interactions between Cu(I) and Bi(III). Additionally, the monometallic analogs (H₂piz)CuI₃ and (H₂piz)Bi₂I₈ reveal the role of heterometallic interactions in modulating the optical properties. This study provides valuable insights into the design of copper–bismuth iodide systems, enriching the library of hybrid materials with customized semiconductor characteristics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130122","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":"Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors","authors":"Manikanta Makala, Zhuang Xu, Shamil Saiev, Xiaojuan Ni, Sina Sabury, Veaceslav Coropceanu, Jean-Luc Brédas, Ying Diao, John R. Reynolds, Oana D. Jurchescu, Anna M. Österholm","doi":"10.1021/acs.chemmater.5c00631","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00631","url":null,"abstract":"In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure–property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for high-performance organic electronic materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122653","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":"High-Pressure States of the Au25 Cluster","authors":"Camino Martín-Sánchez, Khadijetou Ahmed Ethmane, Abolfazl Ziarati, Daniele Rosa-Gastaldo, Michal Swierczewski, Arnulf Rosspeintner, Thomas Bürgi","doi":"10.1021/acs.chemmater.5c00755","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00755","url":null,"abstract":"In the present work, the effects of pressure on the electronic, vibrational, and structural properties of neutral and negatively charged Au₂₅(SR)₁₈ clusters are investigated up to 15 GPa combining UV–vis absorption and Raman spectroscopy. We show that Au₂₅(SR)₁₈ clusters undergo three structural transitions in the 0–15 GPa range located at around 0.8, 6, and 11 GPa. Results indicate that these phase transitions are intrinsic to the M₂₅(SR)₁₈ structure and independent of the pressurization conditions, type of ligand, and charge state. The reported Raman measurements show that vibrational spectroscopy is a powerful tool for structural tracking of atomically precise metal nanoclusters under the application of pressure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"34 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114487","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":"Covalent Tethers and Peptide Side Chains Enable Rapid Exciton Diffusion in One-Dimensional Perylenebisimide Aggregates","authors":"Danielle M. Cadena, Victor Paulino, Seth R. Allen, Jarek A. Maleszka, Ifigeneia Tsironi, Daniel A. Darbah, Jean-Hubert Olivier, Sean T. Roberts","doi":"10.1021/acs.chemmater.5c00336","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00336","url":null,"abstract":"Molecular aggregates containing π-conjugated organic molecules have emerged as promising materials for use in light-harvesting systems due to their ability to transport energy and charge over long distances and along specified dimensions. However, the assembly of these materials into structures with distinct photophysical properties is often guided by noncovalent interactions that are shaped by their environment, making these structures fragile to environmental perturbations. Here, we show that by introducing covalent ethylene glycol tethers to perylenebisimide (PBI) aggregates following their self-assembly, we can create robust structures that can withstand perturbations to their environment while maintaining fast exciton transport. By reducing the length of the tethers and introducing peptide side groups to the PBI units, we can increase the electronic coupling between neighboring PBIs and accelerate exciton transport. Our work shows that stapling supramolecular aggregates postassembly provides a viable strategy for creating robust molecular assemblies that rapidly transport energy.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"78 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114485","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":"Competing Octahedral Modes in the Hybrid Improper Ruddlesden–Popper Ferroelectric Ln2SrSc2O7","authors":"Yu Lu Wei, Zhe Guo, Zheng Duan Zhang, Jiamin Lin, Diming Xu, Yuhui Huang, Xue-Zeng Lu, Xiao Qiang Liu, Xiang Ming Chen","doi":"10.1021/acs.chemmater.5c00325","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00325","url":null,"abstract":"The ferroelectric polarization in hybrid improper ferroelectrics (HIFs) is induced by the combination of oxygen octahedral in-plane rotation (OOR) and out-of-plane tilting (OOT) in perovskite-like structures. Specifically, the widely reported <i>A</i>2₁<i>am</i> phase is established by the one-component order parameters (OPs) of the OOR and the OOT in the double-layered Ruddlesden–Popper compounds. In the present work, an unexpected polar <i>P</i>2₁<i>am</i> phase is identified in <i>Ln</i>₂SrSc₂O₇ (<i>Ln</i> = Pr, Nd, Sm) ceramics, showing a one-component OP of the OOT and a two-component OP of the OOR and thus leading to the coexistence of the polar and antipolar distortions within the phase. The room-temperature ferroelectricity is approved by the well-defined ferroelectric polarization–electric field hysteresis loops. In situ diffraction analysis reveals a phase transition to the nonpolar <i>Amam</i> phase at high temperatures. The magnitude of ferroelectric polarization is significantly influenced by the degree of A-site cation disorder and the tolerance factor, while the Curie temperature exhibits a linear increase with a decreasing tolerance factor, independent of the degree of A-site cation disorder. This work emphasizes the critical role of complicated oxygen octahedral distortions and offers a strategic pathway for the rational design of advanced HIF materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"137 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114486","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":"Media Polarity Control Strategy to Tailor Mechanical Behavior of Dual Monomer Single Network Hydrogels and Integrated Machine Learning Approach","authors":"Subhankar Mandal, Shrinkhala Anand, Dipankar Mandal, Akhoury Sudhir Kumar Sinha, Umaprasana Ojha","doi":"10.1021/acs.chemmater.5c00418","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00418","url":null,"abstract":"Facile and scalable procedures to enhance the toughness of hydrogels and tailor their material behavior simultaneously are notably limited in the literature. Especially, one-pot gelation of dual/multi monomer systems suffers from the issue of macrophase separation, which compromises the mechanical behavior of the resulting hydrogels. In this article, a facile media polarity control strategy is reported to enhance the stretchability and adhesive strength of a dual monomer single network hydrogel by promoting phase mixing in a one-pot procedure. As a proof of concept, acrylamidomethylpropanesulfonic acid and acrylamide (AAm)-based dual monomer single network hydrogel are synthesized in an isopropyl alcohol (IPA)/H₂O mixture and evaluated. The resulting hydrogel (PAMSAAm-IP0.1) exhibits superior extensibility (ε, 1050%), tensile strength (UTS, 110 kPa), and adhesive strength (0.25 MPa) compared to that of the control synthesized in H₂O (ε ≈ 230%, UTS ≈ 70 kPa and adhesive strength ≈ 0.03 MPa), supporting the viability of the strategy. Importantly, these compositions having IPA in the matrix retain their functional behavior at low temperature conditions, suggesting their viability under the said conditions. Subsequently, a number of hydrogel compositions are derived using various solvent mixtures, and a machine learning approach is utilized to predict the tensile behavior of the hydrogels based on the compositional ratios and cross-linking conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104307","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":"Correlation between the Coherence Length and Ionic Conductivity in LiNbOCl4 via the Anion Stoichiometry","authors":"Jon A. Newnham, Jędrzej Kondek, Johannes Hartel, Carolin Rosenbach, Cheng Li, Vasiliki Faka, Lara Gronych, Dana Glikman, Florian Schreiner, Domenik D. Wind, Björn Braunschweig, Michael Ryan Hansen, Wolfgang G. Zeier","doi":"10.1021/acs.chemmater.5c00627","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00627","url":null,"abstract":"LiNbOCl₄ is a recently reported material with high Li⁺ conductivities of ∼10 mS·cm^–1 at room temperature. Here, we explore how changing the anion ratio and the Li⁺ content in the Li_1–<i>x</i>NbO_1–<i>x</i>Cl_4+<i>x</i> series (−0.4 ≤ <i>x</i> ≤ 0.2) affects the ionic conductivity of the material. In doing so, we find that the maximum coherence length and ionic conductivity of LiNbOCl₄ are highly dependent on the O^2–/Cl^– anion ratio in the material. Specifically, we show that, while an amorphous phase fraction of LiNbOCl₄ remains constant throughout the substitution series, any excess of O^2– results in a rapid decrease in the maximum coherence length of the crystaline fraction in each sample. Through a combination of diffraction and spectroscopic techniques, we show that this occurs because the O^2– anions cannot exist on the terminal sites of the [NbOCl₄]_∞^– chains in the material, even when it is made with an excess of O^2– resulting in a shortening of those chains. In contrast, it was observed that Cl^– can occupy the bridging sites resulting in a dependence of the coherence length to the anion ratio. As such, the ionic conductivity of LiNbOCl₄ can be maximized by controlling the maximum coherence length in the material through the anion ratio. Notably, we achieved high ionic conductivities for LiNbOCl₄ consistent with literature reports only when the material was slightly Li⁺ and O^2– deficient, suggesting that the literature samples may also have been off-stoichiometry. In addition, we highlight the features missing from the current structural models of LiNbOCl₄ including the presence of mixed Cl^–/O^2– sites, even in the stoichiometric material, which were previously thought to not exist. Finally, we show that slightly reducing the Li⁺ and O^2– contents in LiNbOCl₄ also translates to higher capacities when it is used as a catholyte in solid-state batteries. These findings show the importance of careful control of the stoichiometry in LiNbOCl₄ to optimize its properties and highlights the potential of LiNbOCl₄ for use as a catholyte in solid-state batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase Stability and Structural Transition of Emergent Topological Superconductor Candidate 2M-WS2","authors":"Mingxin Mao, Hongyi Li, Yuqiang Fang, Aoshen Yang, Xiangyu Bi, Caiyu Qiu, Fuqiang Huang, Hongtao Yuan","doi":"10.1021/acs.chemmater.5c00548","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00548","url":null,"abstract":"2M-WS₂ is a promising topological superconductor candidate with a high superconducting transition temperature that holds Majorana bound states and provides an important material platform for application potentials in topological quantum computing. However, the metastable 2M-WS₂ undergoes a phase transition to be semiconducting 2H-WS₂ under specific conditions, degrading the quality of the sample. Here, we demonstrate the temperature and thickness dependence of the 2M-to-2H structural phase transition of the 2M-WS₂ nanoflake based on Raman spectroscopy measurements. The critical temperature of such a phase transition decreases as the thickness of the 2M-WS₂ nanoflake increases, indicating a negative impact on the performance of 2M-WS₂-based electronic devices. Interestingly, laser irradiation can also induce such a 2M-to-2H structural transition, and the critical laser power to induce such a transition depends on the substrate of 2M-WS₂ nanoflakes, which is consistent with our simulation results. Our findings pave the way toward the fabrication of practical electronic devices based on 2M-WS₂ nanoflakes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087960","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}