Chemistry of Materials最新文献

{"title":"Defect-Triggered Reversible Phase Transformation for Boosting Electrochemical Performance of Coordination Polymers","authors":"Yixiu Xu, Chenyu Yang, Yi Man, Xinwen Dou, Xin Xiao, Qiang Xu, Qiang Ju, Qinghua Liu, Zhenlan Fang","doi":"10.1021/acs.chemmater.4c01957","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01957","url":null,"abstract":"Coordination polymers (CPs) hold promise for reliable and powerful supercapacitors (SCs) to overcome the energy crisis. However, CP-SCs face the daunting challenge of maintaining high pseudocapacitance after long-term charge/discharge cycling. Generally, if introducing defects exerted a positive effect on the property, eliminating defects would show a negative effect, and vice versa. Contrary to this common sense, here we demonstrate that both implanting defects and eliminating defects can significantly boost the specific capacitance of the defect-engineered CPs (DECPs), which are about 1.23 and 1.62 times that of the pristine CP, respectively, without loss of rate capability even after 10,000 charge–discharge cycles. The aqueous (A-ASC) and solid-state asymmetric supercapacitor (SS-ASC) devices based on DECPs deliver high energy densities of 80.3 and 61.5 Wh kg^–1, superb power densities of 8471.0 and 8430.6 W kg^–1, and long cycling lifespan of up to 2000 cycles with 92.0 and 80.0% capacity retention, respectively. Moreover, the SS-ASC exhibits excellent flexibility, verified by 99.0% maintenance of its initial capacitance when it is twisted and bent at 180°. Importantly, this work has certified that stepwise increasing/decreasing the concentration of ordered defects gradually triggered reversible phase transformation of CP from nonporous to microporous by charge–discharge cycling, in situ addition of the modulator, and postsynthetic treatment. The mechanism of forming/eliminating defects and their effects on supercapacitive performances of CP-SCs have been unprecedentedly clarified. These findings offer insight into the relationship between defective structure and electrochemical behavior for developing efficient long-cycling CP-SCs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487810","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":"Cooperative Transport of Lithium in Disordered Li10MP2S12 (M = Sn, Si) Electrolytes for Li-Ion Batteries","authors":"Vinay Maithani, Sumantra Das, Sankha Mukherjee","doi":"10.1021/acs.chemmater.4c01791","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01791","url":null,"abstract":"Disorder in sulfide solid-state electrolytes significantly impacts chemical bonding, affecting electrochemical properties and interface stability. Li₁₀GeP₂S₁₂, a prominent sulfide electrolyte, is expensive and has limited interfacial stability, so substituting Ge with earth-abundant elements, such as Sn and Si, could be more practical. However, a thorough understanding of the kinetics and chemical bonding nature of Li in the Sn/Si-substituted systems is missing owing to the complexity associated with disordered sublattice in these materials. We use isothermal–isobaric ensemble Car–Parrinello molecular dynamics to evaluate configuration-dependent tracer and charged diffusivities and activation energies for lithium-ion migration in disordered configurations of Li₁₀SiP₂S₁₂ (LSiPS) and Li₁₀SnP₂S₁₂ (LSnPS) obtained using ensemble statistics. The study uses Li-ion probability density and maximally localized Wannier orbital analysis to determine how temperature and Sn and Si cations affect Li-ion migration. Our findings indicate that higher temperatures enhance Li-ion mobility by enabling more diffusion pathways. The disordered LSiPS and LSnPS electronic structure shows a Kohn–Sham band gap of 2.4 eV for LSiPS and 2 eV for LSnPS, of the most probable configuration across 500 configurations, suggesting a wider electrolyte window for LSiPS. Additionally, Wannier function visualizations demonstrated the significant impact of locality and temperature on the dynamic nature of bonding states of migrating Li ions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487807","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":"Synthesis and Evaluation of Polymer-Drug Conjugates as Potential Antioxidants and Cholinesterase Inhibitors for Neurodegenerative Diseases","authors":"Nuruddin Mahadik, Gemma A. Barron, Paul Kong Thoo Lin, Colin J. Thompson","doi":"10.1021/acs.chemmater.4c01767","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01767","url":null,"abstract":"Polymer-drug conjugates (PDCs) may offer improved water-solubility and <i>in vitro</i> activity of potential antioxidant and cholinesterase (ChE) inhibitor drugs compared to the drugs alone. Conjugation of these potential drugs to water-soluble polymers could increase their therapeutic efficacy. Vanillin was conjugated to poly(allylamine hydrochloride) (NM10 and NM15) and naphthalimidohexylamine (HEXNAP) was conjugated to poly(acrylic acid) (N5 and N10). The antioxidant and cholinesterase inhibitory activities of these novel PDCs were evaluated and compared with those of their respective starting materials. Additionally, <i>in silico</i> molecular modeling studies were conducted to explore the potential cholinesterase inhibitory mechanisms of these conjugates. NM15 (unadjusted and adjusted value) showed significantly enhanced <i>in vitro</i> antioxidant activity (<i>p</i> ≤ 0.0001) compared to vanillin. The adjusted value of N5 compared to HEXNAP showed significantly enhanced <i>in vitro</i> cholinesterase inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) (<i>p</i> ≤ 0.0001). Kinetic and molecular modeling studies revealed that N5 was a competitive inhibitor of butyrylcholinesterase and interacted with the active sites of human acetylcholinesterase and human butyrylcholinesterase enzymes. NM15 and N5 were identified as lead PDCs based on their enhanced antioxidant and cholinesterase inhibitory activity, respectively. Overall, this work demonstrates the potential use of PDCs as treatment options for neurodegenerative diseases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487808","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-Site Cation Chemistry in Halide Perovskites","authors":"Matthew P. Hautzinger, Willa Mihalyi-Koch, Song Jin","doi":"10.1021/acs.chemmater.4c02043","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02043","url":null,"abstract":"Metal halide perovskites are an important class of semiconductors now being implemented as photovoltaic absorbers and explored for light emission, among other device applications. The semiconducting properties of halide perovskites are deeply intertwined with their composition and structure. Specifically the symmetry, tilting, and distortions of the metal halide octahedra impact the band structure and other optoelectronic properties. In this review, we examine the various compositions of monovalent A-site cations in three-dimensional (3D) halide perovskites AMX₃ (M = divalent metal; X = halide). We focus on how the A-site cation templates the inorganic metal-halide perovskite framework, resulting in changes in the crystal structure symmetry, as well as M–X bonding parameters, summarized in a comprehensive table of AMX₃ structures. The A-site cation motion, effects of alloying, and 2D Ruddlesden–Popper perovskite structures with unique A-site cations are further overviewed. Correlations are shown between these A-site cation dominated structural parameters and the resulting optoelectronic properties such as band gap. This review should serve as a reference for the A-site cation structural chemistry of metal halide perovskites and inspire continued research into less explored metal halide perovskite compositions and structures.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488782","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":"Comparison of Lithium Diffusion in Isostructural Ta12MoO33 and Nb12MoO33: Experimental and Computational Insights from Single Crystals","authors":"Md Abdullah Al Muhit, Sean C. Wechsler, Zachary J. L. Bare, CJ Sturgill, Navindra Keerthisinghe, Matthias A. Grasser, Gregory Morrison, Christopher Sutton, Morgan Stefik, Hans-Conrad zur Loye","doi":"10.1021/acs.chemmater.4c02118","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02118","url":null,"abstract":"The demand for fast charging requires high-performance battery materials with improved ionic transport. Wadsley–Roth (WR) structures have garnered attention, where the combination of blocks and shear planes addresses ionic and electronic conductivity, respectively. An improved understanding of structure–property relationships could lead to higher-performance materials. Herein, we report the first single-crystal structures of Nb₁₂MoO₃₃ and Ta₁₂MoO₃₃ that are consistent with other (3 × 4 × ∞) WR phases. The lithiation of Ta₁₂MoO₃₃ is reported to enable an isostructural comparison with Nb₁₂MoO₃₃. These two compounds have similar unit cell volumes and atomic radii, where the Ta₁₂MoO₃₃ unit cell is 0.2 vol % smaller. Despite the similarities in structure, the lithiation capacities, voltage windows, C rate-dependent capacities, and ionic diffusivities are distinctly different. These experimental trends align well with density functional theory calculations showing (1) a lower activation energy for Li transport within Ta₁₂MoO₃₃ consistent with its measured 1.5–4.9-fold higher diffusion coefficients (lithiation) and (2) an ∼25% greater measured lithiation stoichiometry for Nb₁₂MoO₃₃, which is attributed to the calculated smaller octahedral distortions (compared to Ta₁₂MoO₃₃). These findings reveal that smaller channels in Ta₁₂MoO₃₃ stabilize the transition state with 5-fold coordination, which both decreases the activation energy for diffusion and limits the extent of lithiation. Such structure–property trends help in the search for next-generation battery materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486481","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 Alkali Metal Coordination on the Photoluminescence Quantum Efficiency Trend in Hybrid Supramolecular Trimetallic Halides","authors":"Pan Wang,&nbsp;Jiawei Lin,&nbsp;Zhu Guo and Lingling Mao*,&nbsp;","doi":"10.1021/acs.chemmater.4c0212810.1021/acs.chemmater.4c02128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02128https://doi.org/10.1021/acs.chemmater.4c02128","url":null,"abstract":"<p >Hybrid supramolecular trimetallic halides with a double-shell clathrate structure belong to a type of functional material with complex compositions and wide tunability. The double-shell structure is generally composed of a crown ether molecule sandwiched between different metal halide units. Here, we synthesize six new hybrid trimetallic halides and their solid solutions with the general formula [(<i>A</i>18C6)₃<i>MX</i>₄][<i>BX</i>₄] (where <i>A</i> = K⁺, Rb⁺, Cs⁺; M = Mn²⁺ or Mn_1–<i>x</i>Zn_{<i>x</i>²⁺}; <i>B</i> = In³⁺; <i>X</i> = Cl^– or Br^–), abbreviated as <i>A</i>-<i>M</i>-<i>X</i>. Through the structural analysis of the crystal structure and characterizations of the optical properties of these materials, we have found a direct correlation between the photoluminescence quantum yield (PLQY) and the suitability of the coordination between the <i>A</i>-site metal and the crown ether. Specifically, as the radius of the alkali metal increases (from K to Rb), the PLQY decreases due to poorer suitability. The suitability of the coordination has been analyzed in detail by quantifying the structural parameters (i.e., <i>A</i>–O bond distance, O–<i>A</i>–O bond angle, and distance from <i>A</i> metal to the crown ether center). This trend has been further confirmed via two independent systems using solid solutions through <i>M</i>-site alloying and comparing the chloride and bromide analogs. Surprisingly, a selective coordination mode has surfaced when alloying on the A-site, where the larger alkali metal preferentially coordinates with the connected crown ether instead of the isolated one. This effective approach leads to a wide range of tunability of the PLQY from 21.7 to 95.2% within the total 12 materials. Through further analysis, we have found that the substitution of the <i>A</i>-site metal from K to Cs increases the Mn–<i>X</i> distance, which weakens the crystal field strength of Mn and aligns with the observed trend in PLQY. Our work has further expanded the material space of hybrid trimetallic double-shell clathrates and provides determining insights into controlling the structure and PLQY.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608764","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 Alkali Metal Coordination on the Photoluminescence Quantum Efficiency Trend in Hybrid Supramolecular Trimetallic Halides","authors":"Pan Wang, Jiawei Lin, Zhu Guo, Lingling Mao","doi":"10.1021/acs.chemmater.4c02128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02128","url":null,"abstract":"Hybrid supramolecular trimetallic halides with a double-shell clathrate structure belong to a type of functional material with complex compositions and wide tunability. The double-shell structure is generally composed of a crown ether molecule sandwiched between different metal halide units. Here, we synthesize six new hybrid trimetallic halides and their solid solutions with the general formula [(<i>A</i>18C6)₃<i>MX</i>₄][<i>BX</i>₄] (where <i>A</i> = K⁺, Rb⁺, Cs⁺; M = Mn²⁺ or Mn_1–<i>x</i>Zn_{<i>x</i>²⁺}; <i>B</i> = In³⁺; <i>X</i> = Cl^– or Br^–), abbreviated as <i>A</i>-<i>M</i>-<i>X</i>. Through the structural analysis of the crystal structure and characterizations of the optical properties of these materials, we have found a direct correlation between the photoluminescence quantum yield (PLQY) and the suitability of the coordination between the <i>A</i>-site metal and the crown ether. Specifically, as the radius of the alkali metal increases (from K to Rb), the PLQY decreases due to poorer suitability. The suitability of the coordination has been analyzed in detail by quantifying the structural parameters (i.e., <i>A</i>–O bond distance, O–<i>A</i>–O bond angle, and distance from <i>A</i> metal to the crown ether center). This trend has been further confirmed via two independent systems using solid solutions through <i>M</i>-site alloying and comparing the chloride and bromide analogs. Surprisingly, a selective coordination mode has surfaced when alloying on the A-site, where the larger alkali metal preferentially coordinates with the connected crown ether instead of the isolated one. This effective approach leads to a wide range of tunability of the PLQY from 21.7 to 95.2% within the total 12 materials. Through further analysis, we have found that the substitution of the <i>A</i>-site metal from K to Cs increases the Mn–<i>X</i> distance, which weakens the crystal field strength of Mn and aligns with the observed trend in PLQY. Our work has further expanded the material space of hybrid trimetallic double-shell clathrates and provides determining insights into controlling the structure and PLQY.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487135","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":"Comparison of Lithium Diffusion in Isostructural Ta12MoO33 and Nb12MoO33: Experimental and Computational Insights from Single Crystals","authors":"Md Abdullah Al Muhit,&nbsp;Sean C. Wechsler,&nbsp;Zachary J. L. Bare,&nbsp;CJ Sturgill,&nbsp;Navindra Keerthisinghe,&nbsp;Matthias A. Grasser,&nbsp;Gregory Morrison,&nbsp;Christopher Sutton*,&nbsp;Morgan Stefik* and Hans-Conrad zur Loye*,&nbsp;","doi":"10.1021/acs.chemmater.4c0211810.1021/acs.chemmater.4c02118","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02118https://doi.org/10.1021/acs.chemmater.4c02118","url":null,"abstract":"<p >The demand for fast charging requires high-performance battery materials with improved ionic transport. Wadsley–Roth (WR) structures have garnered attention, where the combination of blocks and shear planes addresses ionic and electronic conductivity, respectively. An improved understanding of structure–property relationships could lead to higher-performance materials. Herein, we report the first single-crystal structures of Nb₁₂MoO₃₃ and Ta₁₂MoO₃₃ that are consistent with other (3 × 4 × ∞) WR phases. The lithiation of Ta₁₂MoO₃₃ is reported to enable an isostructural comparison with Nb₁₂MoO₃₃. These two compounds have similar unit cell volumes and atomic radii, where the Ta₁₂MoO₃₃ unit cell is 0.2 vol % smaller. Despite the similarities in structure, the lithiation capacities, voltage windows, C rate-dependent capacities, and ionic diffusivities are distinctly different. These experimental trends align well with density functional theory calculations showing (1) a lower activation energy for Li transport within Ta₁₂MoO₃₃ consistent with its measured 1.5–4.9-fold higher diffusion coefficients (lithiation) and (2) an ∼25% greater measured lithiation stoichiometry for Nb₁₂MoO₃₃, which is attributed to the calculated smaller octahedral distortions (compared to Ta₁₂MoO₃₃). These findings reveal that smaller channels in Ta₁₂MoO₃₃ stabilize the transition state with 5-fold coordination, which both decreases the activation energy for diffusion and limits the extent of lithiation. Such structure–property trends help in the search for next-generation battery materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608763","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":"Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions","authors":"Nikolaos Chalmpes, Iosif Tantis, Ahmed Wasel Alsmaeil, Athanasios B. Bourlinos, Emmanuel P. Giannelis","doi":"10.1021/acs.chemmater.4c02091","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02091","url":null,"abstract":"We report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH₄). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (<i>E</i>_1/2) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive <i>E</i>_1/2 (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of <i>E</i>_1/2 and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449947","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":"Layered and Low-Dimensional Lead, Silver, and Bismuth Halide Perovskites Directed by Halogen-Substituted Spacer Cations","authors":"Jonathan Schimmels,&nbsp;Willa Mihalyi-Koch*,&nbsp;Chris R. Roy,&nbsp;Kyana M. Sanders,&nbsp;John C. Wright and Song Jin*,&nbsp;","doi":"10.1021/acs.chemmater.4c0208310.1021/acs.chemmater.4c02083","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02083https://doi.org/10.1021/acs.chemmater.4c02083","url":null,"abstract":"<p >Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (<i>e.g</i>., Pb²⁺) to multivalent metals (<i>e.g</i>., Ag⁺ and Bi³⁺), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ)₂PbBr₄, (2ClBZ)₃PbI₅, and (3Cl2FBZ)₂PbI₄, and compare them to their silver and/or bismuth analogs (2ClBZ)₄AgBiBr₈, (3Cl2FBZ)₄AgBiBr₈, (2ClBZ)₃Bi₂I₉, and (3Cl2FBZ)₄Bi₂I₁₀. In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ)₄Bi₂I₁₀ crystallizes in the noncentrosymmetric space group <i>Cmc</i>2₁ and exhibits second-harmonic generation (SHG). The organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608334","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}