Inorganic Chemistry最新文献

Dynamic Luminescence Color Tuning and Afterglow Modulation in Sb3+-Doped 0D Hybrid Perovskite (3-AMB)2CdCl4 Through Controlled Energy Transfer Sb3+掺杂0D杂化钙钛矿（3-AMB）2CdCl4的动态发光调色及余辉调制

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c03418

Xia Liu,Hu Wang,Chenyang Zhang,Yuexiao Pan,Jing Xiong,Meiran Zhang

{"title":"Dynamic Luminescence Color Tuning and Afterglow Modulation in Sb3+-Doped 0D Hybrid Perovskite (3-AMB)2CdCl4 Through Controlled Energy Transfer","authors":"Xia Liu,Hu Wang,Chenyang Zhang,Yuexiao Pan,Jing Xiong,Meiran Zhang","doi":"10.1021/acs.inorgchem.6c03418","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03418","url":null,"abstract":"The development of advanced luminescent materials with tunable emission properties and multidimensional information encoding capabilities has become increasingly promising for next-generation optoelectronic devices and anticounterfeiting technologies. Herein, we reported a novel zero-dimensional (0D) organic–inorganic hybrid metal halides (OIHMHs), (3-AMB)2CdCl4 ([3-AMB]+ = methyl 3-aminobenzoate), and demonstrated how Sb3+ doping enables dual-mode luminescence engineering. Photoluminescence studies revealed excitation-wavelength-dependent color tuning: under 345 nm excitation, emission evolves from blue to orange, while 365 nm excitation yields color variation ranging from deep blue through white to pale yellow. Remarkably, the host exhibits 6 s room-temperature phosphorescence (RTP). The Sb3+ doping enables tunable yellow Sb3+-STEs delayed fluorescence, and achieves time-resolved color switching from yellow to green simultaneously. This work established a paradigm for engineering multifunctional luminescent materials, offering transformative potential for advanced optical encryption and intelligent anticounterfeiting technologies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tuned 4,7-Methoxy-Derivatized DAPhen Ligands with Enhanced Selectivity for Am/Eu and An/Np Separations 调谐4,7-甲氧基衍生达芬配体对Am/Eu和An/Np分离的选择性增强

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c03342

Shi Lin Zhang,Lu Yu,Yong Qiang Wan,Yang-Yang Zhang,Huai Xin Hao,Zhi Peng Wang,John F. Gallagher,Jun Li,Pavle Mocilac

{"title":"Tuned 4,7-Methoxy-Derivatized DAPhen Ligands with Enhanced Selectivity for Am/Eu and An/Np Separations","authors":"Shi Lin Zhang,Lu Yu,Yong Qiang Wan,Yang-Yang Zhang,Huai Xin Hao,Zhi Peng Wang,John F. Gallagher,Jun Li,Pavle Mocilac","doi":"10.1021/acs.inorgchem.6c03342","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03342","url":null,"abstract":"We report the synthesis and evaluation of two CHON-compliant 4,7-dimethoxy-1,10-phenanthroline-2,9-dicarboxamide (DADOMePhen) ligands: an aromatic variant, Et-Tol-DADOMePhen (1), and an aliphatic analogue, TCH-DADOMePhen (2). Solvent extraction under SANEX conditions shows that ligand 1 has good Am/Eu selectivity in an optimal window of 0.1–0.5 M HNO3, achieving a maximum SFAm/Eu of 108.2 at 0.5 M HNO3, the highest reported for a lipophilic ligand of pure DAPhen-type molecular architecture to date. This performance inverts conventional acidity dependence: electron-donating methoxy substituents enhance metal–ligand covalency at low acidity but make the ligand susceptible to protonation at higher concentrations. Coordination and fluorescence studies indicate a 1:2 metal-to-ligand stoichiometry; single-crystal diffraction reveals the structure of ligand 1. Quantum-chemical calculations establish that methoxy groups tune electrostatic potential and frontier orbitals, strengthening bonding relative to parent Et-Tol-DAPhen. Beyond Am/Eu partitioning, ligand 1 may enable actinide/neptunium separations: at 0.1 M HNO3, calculated SFAm/Np, SFPu/Np, SFU/Np, and SFTh/Np reach 436, 1690, 9766, and 1953, respectively, reflecting mismatch between the dioxo Np(V) monocation and the ligand. This work establishes 4,7-methoxy derivatization as a design strategy to tune DAPhen-based extractant selectivity and introduces a ligand that could be useful for specialized low-acidity actinide/neptunium or lanthanide separations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dynamic Balance between Heptamolybdate and Octamolybdate: Controlled Syntheses of Ag46 and Ag48 Nanoclusters and Their Transformation via pH-Regulated Ligand Exchange 七胺钼酸盐和八胺钼酸盐之间的动态平衡：Ag46和Ag48纳米簇的受控合成及其通过ph调节配体交换的转化

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c04316

Jin-Ping Gao,Fu-Qiang Zhang,Xian-Ming Zhang

{"title":"Dynamic Balance between Heptamolybdate and Octamolybdate: Controlled Syntheses of Ag46 and Ag48 Nanoclusters and Their Transformation via pH-Regulated Ligand Exchange","authors":"Jin-Ping Gao,Fu-Qiang Zhang,Xian-Ming Zhang","doi":"10.1021/acs.inorgchem.6c04316","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04316","url":null,"abstract":"The integration of polyoxometalates (POMs) as structural templates for noble metal nanoclusters (NCs) represents a cutting-edge strategy to achieve atomic-level precision in cluster synthesis, but the relationship between polyoxometalates and overall structures of assembled NCs and their transformations often are not clear due to significant complexity coming from transient intermediates and coexisting species. Herein, we report the trifluoroacetic acid (TFA)-mediated controlled syntheses and pH-regulated induced structural transformation of silver NCs: [(Mo7O24)@Ag46(CyhS)28(CF3COO)10(CH3CN)4]•2COOCF3–•2CH3CN and [(Mo8O28)@Ag48(CyhS)24(CF3COO)16(CH3CN)4]•7.5CF3COOH (abbreviated as Ag46 and Ag48). Both clusters feature core–shell architectures with molybdenum-based POMs ([Mo7O24]6– and [Mo8O28]8–) acting as anionic templates directing the assembly of Ag shells. The structural evolution from Ag46 to Ag48 was achieved via pH-regulated ligand exchange, highlighting the dynamic balance between POM cores of different sizes, Ag shell coordination geometry, and TFA’s dual role. This work advances the frontier of hybrid NC-POM systems, offering insights into cluster transformation mechanisms and programmable synthesis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cavity-Forming Cofacial Porphyrin Dimers via Cooperative Zn2+ Binding: Structure, Formation Pathways, and Host Properties 通过Zn2+协同结合形成空腔的共面卟啉二聚体：结构、形成途径和宿主性质

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c05017

Joe Otsuki,Yuto Nakaie,Ryota Yamada,Yosuke Hosoya,Kosuke Sugawa

{"title":"Cavity-Forming Cofacial Porphyrin Dimers via Cooperative Zn2+ Binding: Structure, Formation Pathways, and Host Properties","authors":"Joe Otsuki,Yuto Nakaie,Ryota Yamada,Yosuke Hosoya,Kosuke Sugawa","doi":"10.1021/acs.inorgchem.6c05017","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c05017","url":null,"abstract":"Porphyrins bearing four 2,2′-bipyridine ligands linked through acetylene or diacetylene spacers, ZnPor(C2bpy)4 and ZnPor(C4bpy)4 were designed to self-assemble into cavity-containing cofacial dimers through Zn2+ coordination. Electrospray ionization mass spectrometry confirmed the formation of [(ZnPor(Cnbpy)4)2Zn4]8+ (n = 2, 4). For ZnPor(C2bpy)4, Bayesian Markov chain Monte Carlo (MCMC) analysis of through-space 1H NMR chemical shift changes identified a cofacial dimer as the probable solution structure. Titration of the porphyrins with Zn(OTf)2 produced highly sigmoidal changes in their UV–Vis absorption spectra. Spectral deconvolution by multivariate curve resolution–alternating least-squares, followed by Bayesian MCMC equilibrium analysis, identified the most probable intermediate distributions and supported a stepwise pathway involving side-by-side (J-type) porphyrin dimers before formation of the final cofacial (H-type) dimer. The cavities exhibited spacer-dependent guest selectivity: ZnPor(C2bpy)4 encapsulated electron-deficient aromatic guests through π–π stacking, whereas ZnPor(C4bpy)4 accommodated 4,4′-bipyridine and 4,4′-dipyridylacetylene through ditopic axial coordination. r2SCAN-3c geometry optimizations were consistent with the proposed binding modes. These results establish Bayesian MCMC analysis as a powerful approach for resolving multiparameter systems, including multicomponent supramolecular assemblies, while explicitly accounting for uncertainty.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tetraisopropyl Titanate-Catalyzed Esterification Mechanism for the Synthesis of 1,2-Cyclohexanedicarboxylates 钛酸四异丙酯催化合成1,2-环己二羧酸酯的酯化反应机理

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c03901

Zehua Si,Jing Zhu,Jing Ma,Zitian Guo,Ran Tao,Zhongfeng Geng

{"title":"Tetraisopropyl Titanate-Catalyzed Esterification Mechanism for the Synthesis of 1,2-Cyclohexanedicarboxylates","authors":"Zehua Si,Jing Zhu,Jing Ma,Zitian Guo,Ran Tao,Zhongfeng Geng","doi":"10.1021/acs.inorgchem.6c03901","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03901","url":null,"abstract":"Titanates (e.g., Ti(OiPr)4) serve as green, noncorrosive catalysts for synthesizing the new plasticizer bis(2-ethylhexyl) cyclohexane-1,2-dicarboxylate (DEHCH). However, the structural evolution of the Ti center and the microscopic mechanism remain elusive, hindering industrial process optimization. Herein, we used density functional theory (DFT), coupled with Atoms-in-Molecules (AIM) topological analysis and charge decomposition analysis (CDA), to investigate the diesterification mechanism. The reaction proceeds via four steps: alcoholysis/ligand exchange (ΔG = 36.46 kJ·mol–1); nucleophilic attack of the isooctyloxy group to form a tetrahedral intermediate (ΔG = 65.05 kJ·mol–1); proton transfer to form a tetrahedral geminal diol (ΔG = 36.46 kJ·mol–1); and intramolecular dehydration (ΔG = 156.28 kJ·mol–1). The lower ΔG of alcoholysis relative to the hydrolysis side reaction (48.27–69.74 kJ·mol–1) effectively mitigates water-induced catalyst deactivation. Notably, the Ti atom preferentially activates the isooctyloxy oxygen over the carboxylic carbonyl oxygen, dominating the subsequent nucleophilic attack. AIM and CDA results further reveal dynamic coordination behavior: the Ti center flexibly interconverts between geometries resembling a five-coordinate trigonal bipyramid and a six-coordinate regular octahedron, activating the carboxylic carbonyl oxygen via formation of a partial covalent Ti–O bond. These results suggest that an excess of 2-ethylhexanol (2-EH) not only promotes the desired esterification but also suppresses hydrolysis-induced catalyst deactivation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"46 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Holistic Optimization of Li- and Mn-Rich Cathodes from Precursor Coprecipitation to Mechanochemical Calcination 富锰锂阴极从前驱体共沉淀法到机械化学煅烧的整体优化

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c04183

Yeongin Ok,Aditya Ranjan Pati,Seong-Ah Kim,Hyun Deog Yoo

引用次数: 0

Aromatic Ring-Enhanced Pore-Space-Partitioned Metal–Organic Frameworks for Selective Separation of Saturated Hydrocarbons 芳香环增强孔空间分割金属-有机骨架对饱和烃的选择性分离

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c04893

Jia-Yao Liu,Li-Qiu Yang,Chen-Chen Xing,Zhang-Lei Zhong,Wei Lv,Jing Ma,Quan-Guo Zhai

{"title":"Aromatic Ring-Enhanced Pore-Space-Partitioned Metal–Organic Frameworks for Selective Separation of Saturated Hydrocarbons","authors":"Jia-Yao Liu,Li-Qiu Yang,Chen-Chen Xing,Zhang-Lei Zhong,Wei Lv,Jing Ma,Quan-Guo Zhai","doi":"10.1021/acs.inorgchem.6c04893","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04893","url":null,"abstract":"Light saturated hydrocarbons are difficult to separate efficiently because of their similar physicochemical properties, and metal–organic frameworks (MOFs) with tailor-made pore environments promising adsorbents for precise separation. Here, three aromatic ring-enhanced pore-space-partitioned MOFs (SNNU-304–306) were constructed by integrating thieno[2,3-b]thiophene-2,5-dicarboxylic acid (TDC) with tripyridyl partitioners of different aromatic frameworks and N-site characteristics. Modular variation of the partitioners within the same Ni-TDC framework tunes the cage geometry and local aromatic environment, enabling differentiated recognition of C1–C3 hydrocarbons. SNNU-306 exhibits the highest C2H6 and C3H8 uptakes, with C2H6/CH4 and C3H8/CH4 ideal adsorbed solution theory (IAST) selectivities of 34.1 and 1398.6 at 298 K. More importantly, dynamic breakthrough experiments show that SNNU-304 gives the longest separation time for C2H6/CH4, while SNNU-306 exhibits the longest separation time for C3H8/CH4, demonstrating the targeted regulation of different saturated-hydrocarbon separation requirements by different aromatic partitioners. For the ternary C3H8/C2H6/CH4 mixture, the CH4 purity reaches up to 99.96%. Grand Canonical Monte Carlo (GCMC) simulations reveal that different aromatic partitioners regulate host–guest interactions, thereby enabling differentiated hydrocarbon recognition. These results show that aromatic ring enhancement and pore-space partitioning synergistically transform pacs-MOFs into modularly tunable molecular-recognition systems, offering a strategy for the task-specific design of porous materials for saturated-hydrocarbon separation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"234 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ultrawide NIR-II Emission Regulation of Ni2+ in SrGa12O19 Based on a Crystal-Field Engineering Strategy 基于晶体场工程策略的SrGa12O19中Ni2+的超宽NIR-II发射调控

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c04623

Yi Wei,Yuxin Yang,Wei Wang,Hang Yang,Fuyan Su,Jinxuan Sun,Guogang Li

{"title":"Ultrawide NIR-II Emission Regulation of Ni2+ in SrGa12O19 Based on a Crystal-Field Engineering Strategy","authors":"Yi Wei,Yuxin Yang,Wei Wang,Hang Yang,Fuyan Su,Jinxuan Sun,Guogang Li","doi":"10.1021/acs.inorgchem.6c04623","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04623","url":null,"abstract":"Near-infrared II light (NIR-II, 1000–1700 nm) is highly desirable for deep-tissue bioimaging, nondestructive testing, and night vision, but it remains challenging to realize simultaneously tunable emission peak and bandwidth within a single-activator system. Ni2+ with a 3d8 configuration is a promising broadband NIR-II activator ion whose emission originates from crystal-field-dependent d-d electron transitions. Nevertheless, the currently reported Ni2+-activated phosphors are largely limited with spectral tunability (full width at half-maximum, fwhm <200 nm). Herein, a series of SrGa12O19:Ni2+ phosphors with NIR-II emission are prepared that exhibit an emission peak at 1180 nm originating from the 3T2g → 3A2g electron transition. Through designing Al3+-Ga3+ cation substitution strategy, the local coordination environment and crystal-field strength around Ni2+ are controllably modulated, driving a progressive redshift of the emission peak from 1180 to 1350 nm and a pronounced fwhm broadening from 222 to 566 nm, ultimately affording an ultrabroadband NIR-II emission. Furthermore, a prototype phosphor-converted light-emitting diode (LED) is fabricated, demonstrating promising applications in night vision. This crystal-field engineering strategy substantially extends the tunable range of the emission peak and fwhm for Ni2+-activated phosphors and provides guidelines for optimizing transition-metal-activated NIR luminescent materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"163 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Formation-pH-Dependent Structural Difference as a Significant Control on Ferrihydrite Transformation Behaviors 地层- ph相关结构差异对水合铁相变行为的重要控制

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c03357

Hongyan Wei,Qingze Chen,Shoushu Wei,Haoyang Fu,Jing Liu,Yixuan Yang,Jielong Cao,Jianxi Zhu,Runliang Zhu,Hongping He

{"title":"Formation-pH-Dependent Structural Difference as a Significant Control on Ferrihydrite Transformation Behaviors","authors":"Hongyan Wei,Qingze Chen,Shoushu Wei,Haoyang Fu,Jing Liu,Yixuan Yang,Jielong Cao,Jianxi Zhu,Runliang Zhu,Hongping He","doi":"10.1021/acs.inorgchem.6c03357","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03357","url":null,"abstract":"Ferrihydrite (Fhy) is a metastable iron (oxyhydr)oxide whose transformation into more stable crystalline phases is an important manifestation of its reactivity. However, whether nominally identical 2-line Fhy samples retain formation-dependent differences in short-range structure and how these differences control subsequent phase transformation behavior remain poorly understood. Here, Fhy was synthesized at different pH levels to establish formation-pH-dependent variations in the structure and phase transformation. Although all products were identified as 2-line Fhy by conventional X-ray diffraction, low-pH Fhy contained more hydroxyl-related components and exhibited lower structural order, while the local Fe coordination environments varied with the formation pH. These structural differences strongly affected the subsequent transformation. Under aqueous conditions, Fhy formed at pH 3.0 showed a greater tendency toward dissolution-mediated transformation to goethite, whereas Fhy formed at higher pH values generally yielded a greater relative proportion of hematite. Under nonaqueous conditions, the greater hydroxyl content of low-pH Fhy facilitated dehydroxylation and promoted hematite formation at a lower temperature and shorter reaction time. These results demonstrate that the formation pH leaves a persistent structural imprint on Fhy that governs hydroxylation degrees, Fe coordination environments, and phase transformation pathways. This work establishes formation-controlled short-range structures as a vital determinant of the transformation behavior of metastable materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"497 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multi-B-Site Cation Engineering in Stable Thiocyanate-Templated Layered Double-Perovskite Halides 稳定硫氰酸盐模板层状双钙钛矿卤化物的多b位阳离子工程

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-20 DOI: 10.1021/acs.inorgchem.6c04667

Bhawna,Kanta Ogawa,Koki Matsushima,Takuya Ohmi,Jumpei Ueda,Takafumi Yamamoto

{"title":"Multi-B-Site Cation Engineering in Stable Thiocyanate-Templated Layered Double-Perovskite Halides","authors":"Bhawna,Kanta Ogawa,Koki Matsushima,Takuya Ohmi,Jumpei Ueda,Takafumi Yamamoto","doi":"10.1021/acs.inorgchem.6c04667","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04667","url":null,"abstract":"Hybrid organic–inorganic perovskite halides offer a versatile structural platform owing to their flexible bonding nature. Beyond organic-cation engineering, halide-site engineering using molecular anions has recently emerged as an effective approach to alter the perovskite bonding network; however, accessible compositional and structural diversity remains limited. Here, we report, for the first time, hybrid layered Ag–Bi double perovskites, MA4AgBiX4(SCN)4 (X = Br, I), in which incorporation of thiocyanate (SCN–) at the halide-site reduces perovskite dimensionality. While the previously reported single-metal-cation compound, MA2PbI2(SCN)2, offers a unique van der Waals-coupled structural platform, its rapid decomposition, limited compositional space, and lack of bromide analogue hindered further development. First-principles calculations suggest that the structural instability of the lead-based bromide analogue arises from a bromide-induced lifting of the axial SCN ligand and resultant increased interlayer hydrogen-bond distance. Transitioning to an Ag–Bi architecture mitigates this destabilizing effect, as Ag+ (4d105s0) possesses isotropic s-orbital character and enhanced angular flexibility compared to Pb2+ (6s26p0) with a stronger orientational preference. This strategy yields a full range of solid solutions with band gaps tunable from 1.95 to 2.30 eV. The resulting materials, particularly the bromide-rich phases, exhibit markedly increased environmental robustness, demonstrating that multi-B-site cation design can expand the structural diversity of stable pseudohalide-based hybrid perovskites.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0