Chemistry of Materials最新文献

{"title":"Fabrication of 3D-Printed Carbon Microarchitected Structures with High Yield from Polyacrylonitrile Composites via Gel Infusion and Pyrolysis","authors":"Philip R. Onffroy,&nbsp;, ,&nbsp;Montana Lagat,&nbsp;, ,&nbsp;Dennis Schröder,&nbsp;, ,&nbsp;Jacob A. Dobson,&nbsp;, ,&nbsp;Samuel Chiovoloni,&nbsp;, ,&nbsp;Michael J. Bortner,&nbsp;, ,&nbsp;Jennifer Q. Lu,&nbsp;, ,&nbsp;Max A. Saccone*,&nbsp;, and ,&nbsp;Joseph M. DeSimone*,&nbsp;","doi":"10.1021/acs.chemmater.5c01873","DOIUrl":"10.1021/acs.chemmater.5c01873","url":null,"abstract":"<p >Fabrication of geometrically complex conductive carbon electrodes with micrometer-scale features via polymer 3D printing and pyrolysis enables precise control over precursor composition and structure geometry, enabling the development of a tunable electrode design space for electrochemical systems. Continuous liquid interface production 3D printing of lattices with high surface-to-volume ratios offers promise for producing polymer pyrolysis precursors with tailored microarchitected structures. Herein, a method is reported for 3D printing of polyacrylonitrile-derived carbon structures via gel infusion and subsequent pyrolysis. With optimized pyrolysis conditions, samples demonstrate high char yields of greater than 40% by mass, comparable to yields for conventionally electrospun polyacrylonitrile fibers and higher than commercial resin alternatives. Characterization of polyacrylonitrile-derived 3D carbon lattices reveals carbon crystallite sizes in the nanocrystalline to amorphous regime and capacitance values up to 1.98 F/g corresponding to an electrochemically active surface area (ECSA) of &gt;1 m²/g with solid lattice beams. Increasing the pyrolysis temperature results in a higher ECSA, likely caused by increased surface roughness confirmed by microscopy. This gel infusion and pyrolysis method establishes a platform for incorporation of high char yield linear polymers into high-resolution microarchitected structures, paving a pathway for producing hierarchical 3D electrodes for energy storage, catalysis, and reactor technology applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"8009–8020"},"PeriodicalIF":7.0,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073055","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":"Thin-Film Fracture Behavior for Diketopyrrolopyrrole Semiconducting Polymeric Films","authors":"Song Zhang,&nbsp;, ,&nbsp;Yunfei Wang,&nbsp;, ,&nbsp;Gage T. Mason,&nbsp;, ,&nbsp;Zhiyuan Qian,&nbsp;, ,&nbsp;Simon Rondeau-Gagné,&nbsp;, and ,&nbsp;Xiaodan Gu*,&nbsp;","doi":"10.1021/acs.chemmater.5c01388","DOIUrl":"10.1021/acs.chemmater.5c01388","url":null,"abstract":"<p >Fracture energy, which quantifies a material’s resistance to the propagation of a pre-existing crack, is a key parameter for ensuring the mechanical reliability of stretchable organic electronic devices. However, most existing methods, such as a four-point bending fracture energy, utilized for measuring the fracture energy of semiconducting polymeric thin films are complicated by substrate effects, making it challenging to isolate the intrinsic behavior of the film from interfacial influences. In this study, we employed a pseudo free-standing pure shear method to systematically investigate the cohesive fracture energy of poly(diketopyrrolopyrrole-terthiophene) P(DPP-T)-based thin films to examine the effects of nanoconfinement, side chain length, degree of crystallinity, and strain rates. This method effectively eliminates substrate interference, enabling a direct assessment of the cohesive fracture energy of P(DPP-T) thin films. We found that thinner films and those with lower molecular weights exhibited significantly reduced fracture energies due to diminished chain entanglements. Additionally, films with shorter side chains displayed notably higher fracture energies, which were attributed to an increase in the degree of crystallinity. Finally, slower strain rates led to higher fracture energies, consistent with an enhanced stress relaxation. These insights offer practical guidelines for designing mechanically robust semiconducting polymers, contributing to the advancement of reliable, durable, flexible, and wearable electronic devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"7804–7812"},"PeriodicalIF":7.0,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c01388","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073062","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":"The Role of Terminal Groups in Nonchiral Rod-Like Compounds on the Formation of Polar Fluids","authors":"Michał Czerwiński*,&nbsp;, ,&nbsp;Mateusz Mrukiewicz,&nbsp;, ,&nbsp;Mateusz Filipow,&nbsp;, ,&nbsp;Damian Pociecha,&nbsp;, ,&nbsp;Natalia Podoliak,&nbsp;, ,&nbsp;Dalibor Repček,&nbsp;, ,&nbsp;Monika Zając,&nbsp;, and ,&nbsp;Dorota Węgłowska,&nbsp;","doi":"10.1021/acs.chemmater.5c02109","DOIUrl":"10.1021/acs.chemmater.5c02109","url":null,"abstract":"<p >The emergence of ferroelectric mesophases in nonchiral liquid crystals (LCs) has sparked fundamental interest in the molecular mechanisms governing polarity. In this study, we investigate how terminal molecular groups influence the formation and stability of polar phases by analyzing six compounds from three homologous series. Specifically, we compare synthesized homologues with a nitro group, which predominantly exhibit polar mesophases, to previously reported structurally related analogs containing either a cyano group or a fluorine atom as a terminal fragment. Density functional theory calculations provide insights into electronic surface potential (ESP) distributions, revealing alternating regions of positive and negative charge density along the molecular axis, consistent with Madhusudana’s model of polar phase stabilization. We propose the ESP-derived parameter quantifying terminal electrostatic charge, revealing a direct correlation between the negative-to-positive charge ratio at the molecular termini and the formation of ferroelectric or antiferroelectric mesophases. To validate this hypothesis, we analyze the molecular structure–mesomorphic behavior relationship of other known nonchiral compounds that exhibit polar phases, demonstrating the critical role of terminal groups in determining mesophase polarity. Our findings enhance the understanding of the molecular origins of ferroelectricity in nonchiral LCs, paving the way for the rational design of next-generation functional polar soft materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"8077–8087"},"PeriodicalIF":7.0,"publicationDate":"2025-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c02109","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073058","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":"Histidine–Copper Site Variability in UiO-66: Monitoring Synthetic Intricacy with EPR Spectroscopy","authors":"Erlend Aunan,&nbsp;, ,&nbsp;Isabelle Gerz,&nbsp;, ,&nbsp;Karl P. Lillerud,&nbsp;, ,&nbsp;Serena DeBeer*,&nbsp;, and ,&nbsp;Unni Olsbye*,&nbsp;","doi":"10.1021/acs.chemmater.5c01005","DOIUrl":"10.1021/acs.chemmater.5c01005","url":null,"abstract":"<p >Bioinspired design of catalysts aims to harness natural motifs observed in enzymatic systems to develop more efficient catalysts for industrial applications. One particularly inspiring group of enzymes─monooxygenases─demonstrate the highly efficient partial oxidations of substrates, such as the conversion of methane to methanol, a process that is highly sought after in industrial chemistry. In this study, we explore the use of zirconium-based metal–organic framework UiO-66, synthesized with open zirconium sites, to support copper–histidine complexes of varying geometries and speciation. Through the application of EPR spectroscopy, we identified three distinct copper species within the framework. The mole fractions of these copper species varied depending on the histidine loading, suggesting a tunable system with potential implications for catalytic performance. Without histidine loading, copper was found to bind scarcely to the defective site. With histidine, however, copper retention was improved. Two different species formed, of which one resembles the pMMO Cu_B site. Our findings lay the groundwork for further exploration and development of advanced catalysts using bioinspired design and cutting-edge MOF-characterization techniques.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"7648–7655"},"PeriodicalIF":7.0,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c01005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073063","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":"Mechanical-Fluorescent Bifunctional Smart Crystals: Hydrogen-Bond Engineering for Ultra-Flexible Response and Programmable Thermochromic Switching","authors":"Nanjun Chen,&nbsp;, ,&nbsp;Jiayao Li,&nbsp;, ,&nbsp;Feiqiang He,&nbsp;, ,&nbsp;Zhi Gao,&nbsp;, ,&nbsp;Yun Chen,&nbsp;, ,&nbsp;Limin Zhou,&nbsp;, ,&nbsp;Li Xu,&nbsp;, ,&nbsp;Jerry Heng,&nbsp;, ,&nbsp;Songgu Wu,&nbsp;, and ,&nbsp;Jinbo Ouyang*,&nbsp;","doi":"10.1021/acs.chemmater.5c02008","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02008","url":null,"abstract":"<p >This study successfully synthesized four organic crystalline materials exhibiting dual-functional responses of mechanical behavior and thermochromic fluorescent by introducing halogen atoms and hydrazide structures into CIM crystals via crystal engineering strategies. The LHIH crystals exhibit excellent reversible elastic bending, with a bending strain angle reaching up to 180°. LHIH’s mechanical flexibility stems from the N–H···N interactions in the hydrazone structure, which form a “bridge-like” network of molecules. The resulting slip interfaces and interlocking structure effectively dissipate stress and prevent fracture. At the same time, the CIM, LCIM, BCIM, and BHBH crystals exhibit significant unidirectional fluorescence color switching (e.g., from orange-yellow to dark orange) under thermal stimulation, which is attributed to structural changes caused by temperature-induced lattice distortion. In contrast, the LHIH crystals undergo a unique ternary fluorescence color switching (yellow → dark green → grass green) at a thermal phase transition temperature of 122 °C. This study provides a strategy for the development of multistimuli responsive smart crystals and demonstrates their potential applications in flexible optical sensors, optoelectronic devices, and information encryption.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7492–7502"},"PeriodicalIF":7.0,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117425","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":"Impact of Secondary Phases on the Electrochemical Performance of Li6.4La3Zr1.4Ta0.6O12 Garnet Solid Electrolytes through Grain Boundary Engineering","authors":"Sebastian J. Altus,&nbsp;, ,&nbsp;Innes McClelland,&nbsp;, ,&nbsp;Stephen W. T. Price,&nbsp;, ,&nbsp;Julian S. Dean,&nbsp;, ,&nbsp;Olof Gutowski,&nbsp;, ,&nbsp;Hany El-Shinawi,&nbsp;, ,&nbsp;Samuel G. Booth,&nbsp;, ,&nbsp;Serena A. Cussen*,&nbsp;, and ,&nbsp;Edmund J. Cussen*,&nbsp;","doi":"10.1021/acs.chemmater.5c01195","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01195","url":null,"abstract":"<p >Fast-conducting Li₇La₃Zr₂O₁₂ (LLZO)-type garnet solid-state electrolytes face the considerable challenge of deleterious metallic dendrite formation during operation, with suggestions that this behavior may be linked to electronic conductivity effects. To examine in detail how electronic conductivity effects at the grain boundary can affect the electronic properties of cubic LLZO-type garnets, we report a family of Ta-doped LLZO garnets with a Mn-containing secondary phase, which is spatially selective toward the grain boundaries. The inclusion of this targeted grain boundary phase, whose composition is revealed as La₄LiMnO₈, alters the ionic and local electronic conductivities of the final composite, resulting in improvements in the observed critical current densities. We find that the critical current density before short-circuiting is highly dependent on this secondary phase, increasing with increasing content up to a maximum of 0.30 mA cm^–2. X-ray absorption spectroscopy and X-ray diffraction computed tomography studies complement these findings, revealing that a darkening of the composite electrolyte post cycling is accompanied by Mn reduction and a reduction in the phase fraction of La₄LiMnO₈. Guided by electrochemical characterization and finite element analysis, we highlight the critical role of grain boundaries in bulk garnet degradation pathways and evidence how spatially targeted secondary phases, introduced during initial synthesis, can impact electrochemical performance in LLZO-type garnets.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7136–7146"},"PeriodicalIF":7.0,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c01195","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117396","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":"Hybrid Bismuth(III)-Halide Double Perovskite-Derived Ferroelastic (Pip)2[KBiBr6] with Excitonic and Bi(III) Luminescence due to Electronic Confinement along Inorganic Pillars","authors":"Magdalena N. Rowinska,&nbsp;, ,&nbsp;Oleksandr Korolevych,&nbsp;, ,&nbsp;Adam Kabański,&nbsp;, ,&nbsp;Dagmara Stefanska,&nbsp;, ,&nbsp;Tamara Bednarchuk,&nbsp;, ,&nbsp;Anna Piecha-Bisiorek,&nbsp;, and ,&nbsp;Anna Gagor*,&nbsp;","doi":"10.1021/acs.chemmater.5c01183","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01183","url":null,"abstract":"<p >Organic–inorganic halide double perovskites with the A₂MM′X₆ composition are considered a more stable and environmentally friendly alternative to lead-based APbX₃ compounds (3D HOIPs). Herein, we report the synthesis, crystal structure, physicochemical characterization, and the results of density functional theory (DFT) calculations for a double-perovskite-related (piperidinium)₂[KBiBr₆]. Inorganic structure is built of 1D inorganic pillars composed of Bi(III)Br₆ octahedra face shared with trigonal KBr₆ antiprisms. It undergoes a room-temperature order–disorder phase transition at <i>T</i>_c = 300/303 K (cooling/heating), associated with molecular dynamics and formation of stable hydrogen-bond interactions. Dielectric relaxation in the vicinity of <i>T</i>_c indicates gradual ordering of piperidinium. The <i>C</i>2/<i>m</i> to <i>P</i><i></i><math><mover><mn>1</mn><mo>−</mo></mover></math> symmetry reduction leads to the formation of a switchable ferroelastic domain structure. The material shows purplish-blue photoluminescence from high-energy excitons and Bi(III) emission due to the electronic confinement along the inorganic pillars. DFT calculations of the density of states confirm that the electronic properties are governed by the electronic states of Bi(III)Br₆ octahedra and reveal that electron and hole migration occur between neighboring chains, being quenched along the inorganic part. The optical band gap <i>E</i>_g is 2.8 eV.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7125–7135"},"PeriodicalIF":7.0,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c01183","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117429","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":"A Chiral Hierarchical Helical Covalent Organic Framework for Enantiomeric Separation","authors":"Yun-Qiao Zhao,&nbsp;, ,&nbsp;Yun-Jie Li,&nbsp;, ,&nbsp;Ren-Xiu He,&nbsp;, ,&nbsp;Hao Wang,&nbsp;, ,&nbsp;Tian-Jian Xiong,&nbsp;, ,&nbsp;Bang-Jin Wang,&nbsp;, ,&nbsp;Jun-Hui Zhang,&nbsp;, ,&nbsp;Sheng-Ming Xie*,&nbsp;, and ,&nbsp;Li-Ming Yuan,&nbsp;","doi":"10.1021/acs.chemmater.5c01802","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01802","url":null,"abstract":"<p >Helical covalent organic frameworks (HeliCOFs) are a special type of organic framework material that successfully integrates molecular chirality, channel chirality, and morphological chirality into a single crystalline entity. In this study, a novel P-heliCOF@SiO₂ core–shell composite with uniform particle size and shell thickness was prepared based on an in situ growth synthesis strategy. The shell thickness of the P-heliCOF@SiO₂ microspheres was adjusted by altering the concentration of the catalyst (acetic acid) and the ratio of reactants. The P-heliCOF@SiO₂ microspheres packed column was applied for the resolution of various racemates by HPLC. The P-heliCOF@SiO₂ core–shell composite exhibited excellent resolution performance for 25 pairs of enantiomers such as alcohols, esters, amines, epoxides, ethers, ketones, and organic acids. The effects of sample mass, column temperature, mobile phase composition, and different batches of chromatographic columns on the separation performance were investigated. Compared with the commercial Chiralcel OD-H and Chiralpak AD-H columns, the enantioseparation performance of the P-heliCOF@SiO₂ column shows good complementarity with that of these two widely used commercial columns for these chiral compounds. This chiral column also showed good reproducibility and stability for HPLC enantiomeric separation. This work develops a HeliCOF with hierarchical chirality as a novel chromatographic medium, which will push forward the applications of CCOFs in the field of chiral separation.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7410–7418"},"PeriodicalIF":7.0,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117408","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 Learning Framework for Atomic-Level Polymer Structure Generation","authors":"Ayush Jain,&nbsp;, ,&nbsp;Ashutosh Srivastava,&nbsp;, and ,&nbsp;Rampi Ramprasad*,&nbsp;","doi":"10.1021/acs.chemmater.5c01644","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01644","url":null,"abstract":"<p >Synthetic polymeric materials underpin fundamental technologies in the energy, electronics, consumer goods, and medical sectors, yet their development still suffers from prolonged design timelines. Although polymer informatics tools have supported speedup, polymer simulation protocols continue to face significant challenges in the on-demand generation of realistic 3D atomic structures that respect the conformational diversity of polymers. Generative algorithms for 3D structures of inorganic crystals, biopolymers, and small molecules exist, but have not addressed synthetic polymers because of challenges in representation and data set constraints. In this work, we introduce polyGen, a generative model designed specifically for 3D polymer structures that operates from minimal inputs such as the repeat unit chemistry alone. polyGen combines graph-based encodings with a latent diffusion transformer using positional biased attention for realistic conformation generation. Given the limited data set of 3,855 DFT-optimized polymer structures, we incorporate joint training with small molecule data to enhance generation quality. We also establish structure matching criteria to benchmark our approach on this novel problem. polyGen overcomes the limitations of traditional crystal structure prediction methods for polymers, successfully generating realistic and diverse linear and branched conformations, with promising performance even on challenging large repeat units. As an atomic-level proof-of-concept capturing intrinsic polymer flexibility, it marks a transformative capability in material structure generation.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7337–7346"},"PeriodicalIF":7.0,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c01644","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117246","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":"Tunable Nonlinear Optical Properties in Porphyrin–CdIIBr2 Complexes Functionalized MXenes Featuring Different Configurations","authors":"Lulu Fu,&nbsp;, ,&nbsp;Zihao Guan,&nbsp;, ,&nbsp;Lu Chen,&nbsp;, ,&nbsp;Zhenyi Yan,&nbsp;, ,&nbsp;Zhipeng Huang,&nbsp;, ,&nbsp;Mark G. Humphrey,&nbsp;, and ,&nbsp;Chi Zhang*,&nbsp;","doi":"10.1021/acs.chemmater.5c00892","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00892","url":null,"abstract":"<p >Functional materials displaying profound third-order optical nonlinearities across a wide spectral region and a broad temporal domain are required for feasible signal processing and sophisticated laser conditions. Particularly desirable are the materials with convertible nonlinear optical (NLO) activity toward both nanosecond and femtosecond pulses. Herein, for the first time, tunable NLO performance in MXene–porphyrin composite systems is realized through fine control of the configuration. Two D–A-type porphyrin–terpyridine–Cd^IIBr₂ complexes with asymmetric, configuration-different structures were designed, synthesized, and subsequently incorporated with MXene (Ti₃C₂T_<i>x</i>) nanosheets. In these two samples, porphyrin and the Cd^IIBr₂L unit are mutually perpendicular or parallel to each other due to the benzene ring and the resulting steric hindrance. Both samples exhibit remarkably enhanced optical nonlinearity compared with their untreated samples. Notably, Ti₃C₂T_<i>x</i>–CdCPor (C: coplanar) possesses optimized strong NLO performance with a corresponding nonlinear absorption coefficient (β_eff) of 1.06 × 10³ cm GW^–1 toward the ultrafast femtosecond lasers at 800 nm, while Ti₃C₂T_<i>x</i>–CdOPor (O: orthogonal) exhibits strong reverse saturable absorption when it responds to nanosecond laser irradiation at 532 nm and shows no response to femtosecond lasers. These results demonstrate that the two newly developed MXene composites are very promising optical limiting (OL)candidates for practical applications across wide spectral and temporal domains and that covalently functionalizing MXene-based materials with configuration-different chromophores may be a useful and effective approach to engineering adaptable photonic devices with broad-ranging and feasible NLO activity.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 18","pages":"7026–7036"},"PeriodicalIF":7.0,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117354","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}