Inorganic Chemistry最新文献_第10页

An Amide-Functionalized Pillar-Layered Metal–Organic Framework Based on Mixed Linker Systems with Enhanced Third-Order Nonlinear Optical Performance 基于三阶非线性光学性能增强的混合连接体系的酰胺功能化柱层金属-有机骨架

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-22 DOI: 10.1021/acs.inorgchem.5c03846

Reza Abazari, Marzieh Nadafan, Soheila Sanati, Rajender S. Varma, Jinjie Qian

{"title":"An Amide-Functionalized Pillar-Layered Metal–Organic Framework Based on Mixed Linker Systems with Enhanced Third-Order Nonlinear Optical Performance","authors":"Reza Abazari, Marzieh Nadafan, Soheila Sanati, Rajender S. Varma, Jinjie Qian","doi":"10.1021/acs.inorgchem.5c03846","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03846","url":null,"abstract":"The development of novel nonlinear optical (NLO) materials is increasingly focused on crystal structures that offer both high efficiency and laser damage thresholds, particularly for appliances in optical switching and communications. Herein, an experimental inquiry is described into the third order NLO response of an amide-functionalized pillar-layered metal–organic framework (MOF) encompassing cobalt ions and 4,4′-oxybis(benzoic acid) and N,N′-bis(4-pyridylformamide)-1,4-benzenediamine linkers. The introduced MOF possesses a complex porous structure defined by a 3,4,5T94 topology. The π-conjugated structure and nitrogen-containing derivatives with lone electron pairs on the nitrogen atoms endow this MOF with strong intramolecular charge-transfer capabilities, thereby facilitating the formation of donor–acceptor molecules. The pillared Co-MOF offers a significant nonlinear optical profile, with an NLR index (n2) at a range of (6.6–19.1) × 10–8 cm2/W and an NLA coefficient (β) of (2.92–14.27) × 10–3 cm/W. The rationale explanation for the NLO response in pillared Co-MOFs, could be d–d transitions of Co2+ ions, π–π and LMCT/MLCT transitions, charge-transfer interactions between metal nodes and organic linkers, structural anisotropy, and pillar-induced electron delocalization. The Z-scan findings highlight the potential of the pillared MOFs with mixed ligands as promising alternatives for photonics devices, optical switches, and optical power-limiting technologies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116242","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

Isocyanate Route to Tungsten(VI) Imido Fluorido Complexes. 异氰酸酯制钨（VI）亚酰氟配合物。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-21 DOI: 10.1021/acs.inorgchem.5c03289

Melanie Riethmann,Leonhard Eyßelein,Janis Walpuski,Leon N Schneider,Maik Finze,Udo Radius

{"title":"Isocyanate Route to Tungsten(VI) Imido Fluorido Complexes.","authors":"Melanie Riethmann,Leonhard Eyßelein,Janis Walpuski,Leon N Schneider,Maik Finze,Udo Radius","doi":"10.1021/acs.inorgchem.5c03289","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03289","url":null,"abstract":"A general synthetic route for tungsten(VI) organoimido fluorido complexes is reported, which relies on the key metathesis of organo isocyanates and tungsten(VI) oxo tetrafluoride or its acetonitrile adduct [WOF4(MeCN)]. The reaction of 4-tolyl isocyanate, 2,5-dimethylphenyl isocyanate, benzyl isocyanate, 4-fluorophenyl isocyanate and 4-chlorophenyl isocyanate with [WOF4] or [WOF4(MeCN)] at 100 °C in acetonitrile (MeCN) or tetrahydrofuran (THF) afforded the imido complexes [W(NR)F4(L)] (R = Tol = tolyl = 4-CH3-C6H4, 1; DMP = 2,6-dimethylphenyl = 2,6-(CH3)2-C6H3, 2; Bn = benzyl = CH2-C6H5, 3; FPhen = 4-fluorophenyl = 4-F-C6H4, 4; ClPhen = 4-chlorophenyl = 4-Cl-C6H4, 5) as their MeCN or THF adducts 1(MeCN)-5(MeCN) and 1(THF)-5(THF), respectively. Similarly, treatment of [WOF4(MeCN)] with 1,4-phenylene diisocyanate in acetonitrile afforded the dinuclear complex [{WF4(MeCN)}2{μ-1,4-NC6H4N}] (6(MeCN)). The solvent ligand can be easily replaced, as exemplified for the reaction of 1(MeCN), 4(MeCN), and 5(MeCN) with pyridine (py) or 1(MeCN) with benzophenone (PhCOPh) to yield 1(py), 4(py), 5(py) and 1(PhCOPh). Furthermore, 1(MeCN) and 2(MeCN) react with [NMe4]F and NEt3·3HF to yield the tungstate(VI) imido pentafluorido salts [cat][W(NR)F5] (R = Tol, a; DMP; b; cat = NMe4, 7; NEt3H, 8) 7a-8b.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103546","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

Dual-Emission Lanthanide-MOF Sensors Enabling Ratiometric Fluorescent Detection of 2,4,6-Trinitrotoluene with High Selectivity. 双发射镧系- mof传感器实现了2,4,6-三硝基甲苯的高选择性比例荧光检测。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-21 DOI: 10.1021/acs.inorgchem.5c03421

Wei Lv,Nan Song,Yu-Dong Shao,Quan-Guo Zhai

{"title":"Dual-Emission Lanthanide-MOF Sensors Enabling Ratiometric Fluorescent Detection of 2,4,6-Trinitrotoluene with High Selectivity.","authors":"Wei Lv,Nan Song,Yu-Dong Shao,Quan-Guo Zhai","doi":"10.1021/acs.inorgchem.5c03421","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03421","url":null,"abstract":"Although designing dual-emission probes remains challenging, mixed-ligand metal-organic frameworks (MOFs) offer a promising platform for ratiometric fluorescent sensors. MOFs with multiple components of different metal centers and/or different ligands provide a great chance for the precise synthesis of ratiometric fluorescent sensors. Herein, N,N'-bis(5-isophthalic acid)-naphthalene diimide (NDI) with a large π-conjugate plane was selected to combine with 2,5-dihydroxyterephthalic acid (DHBDC), a typical molecule with an excited-state intramolecular proton transfer process, to form a mixed-ligand system. Their self-assembly with lanthanide metal ions (Ln3+) under solvothermal conditions led to a series of Ln-MOFs, named [Ln(DHBDC)0.5(NDI)0.5·solvents] (SNNU-380(Ln); Ln = Tb, Eu, Er, Dy, Gd, and Nd; solvents = N,N'-dimethylformamide (DMF) and/or N,N'-dimethylpropyleneurea (DMPU)). As expected, SNNU-380(Ln) exhibits controllable dual fluorescence emissions originating from two fluorescent ligands (420 nm emission from NDI and 550 nm emission from DHBDC) mildly regulated by lanthanide metal ions and shows unique fluorescence quenching for selective 2,4,6-trinitrotoluene (TNT) detection through a photoinduced electron transfer (PET) mechanism. Among them, SNNU-380(Eu) exhibits outstanding detection ability with the highest sensitivity (KSV = 6.80 × 103 M-1), the lowest detection limit (0.18 ppm), a rapid response, exceptional selectivity among nitro-aromatic explosives (NAEs), and excellent recyclability, surpassing the performance of most MOF sensors.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103571","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

Modulating Nonlinear Optical Performances in α/β-SnGa2GeS6 Polymorphs via Atomic Coordination Engineering 利用原子配位工程调制α/β-SnGa2GeS6多晶的非线性光学性能

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-20 DOI: 10.1021/acs.inorgchem.5c03960

Jingjing Xu, Yan Xiao, Dazhi Lu, Bingbing Zhang, Kui Wu, Haohai Yu, Huaijin Zhang

{"title":"Modulating Nonlinear Optical Performances in α/β-SnGa2GeS6 Polymorphs via Atomic Coordination Engineering","authors":"Jingjing Xu, Yan Xiao, Dazhi Lu, Bingbing Zhang, Kui Wu, Haohai Yu, Huaijin Zhang","doi":"10.1021/acs.inorgchem.5c03960","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03960","url":null,"abstract":"Property modulation based on structural transformation has emerged as a crucial strategy for developing high-performance nonlinear optical (NLO) crystals. Among them, polymorphic systems with structural diversity and fascinating performances have attracted growing attention in the exploration of NLO materials. In this work, adjusting the coordination environment (from SnS5 to SnS3) of the lone-pair Sn2+ cation enables the discovery of another new phase, β-SnGa2GeS6, which crystallizes in the Cc group that is different from the previously reported α-phase (Fdd2). Detailed characterization reveals distinct NLO properties between the α- and β-polymorphs, including NLO response (α: 17.8 pm/V vs β: 13.7 pm/V) and birefringence (α: 0.151 vs β: 0.126). Theoretical calculations confirm that the reduced NLO response in the β-phase arises from the canceled polarization of the [SnS3] units, as evidenced by dipole moment analysis. This study highlights the influence of atomic coordination engineering in polymorphic systems for structural transition and tunable NLO performances. Such established “phase transition → structural transformation → NLO property” relationship in polymorphs provides a design paradigm for discovering next-generation NLO materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"247 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145088939","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

RECrO3 as High-Contrast Thermochromic Memory Pigments: Enabled by Hydrothermal Distortions and Magnetic Tuning (RE = Eu, Tb, Y) 高对比度热致变色记忆颜料RECrO3：水热变形和磁调谐（RE = Eu, Tb， Y）

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-20 DOI: 10.1021/acs.inorgchem.5c03541

Shan Wang, Fen Chen, Zhaowei Xu, Tianming Zhang, Fanxu Meng, Long Yuan

{"title":"RECrO3 as High-Contrast Thermochromic Memory Pigments: Enabled by Hydrothermal Distortions and Magnetic Tuning (RE = Eu, Tb, Y)","authors":"Shan Wang, Fen Chen, Zhaowei Xu, Tianming Zhang, Fanxu Meng, Long Yuan","doi":"10.1021/acs.inorgchem.5c03541","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03541","url":null,"abstract":"Inorganic crystals synthesized via different methods with the “same” composition often exhibit distinct properties, a phenomenon frequently overlooked or misinterpreted. In this work, we demonstrate the peculiar magnetic properties and thermochromic memory behavior of three perovskite-structure rare-earth chromites (RECrO3, RE = Eu, Tb, and Y) synthesized by a mineralizer-assisted hydrothermal method at 225 °C. The crystals feature an elongated b-axis and greater distortion of the CrO6 octahedral subunits. Crystal shapes are sensitive to the composition, mineralizer concentration, and reaction temperature. Raman and infrared peaks show a RE3+-dependent behavior. All samples are canted-antiferromagnetic with significantly lower Néel temperatures than the samples synthesized via other methods. Three notable magnetic transition points are shown in TbCrO3, which have never been found in other samples. Temperature and magnetic field dependent magnetization curves of EuCrO3 samples show crystal shape dependent magnetic behaviors. All of the samples show continuously irreversible thermochromic properties from 100 to 500 °C with color changes from yellowish green to reddish brown with the highest chromaticity aberration of ΔE = 51.47 in TbCrO3. This work indicates that the materials synthesized via the mineralizer-assisted hydrothermal crystallization method facilitate versatile tunability of the structure and physical properties with promising thermal recording applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089387","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

Facial and Meridional PNN-Ruthenium Pincer Complexes in Base-Free Nitrile Hydration with Concurrent Ligand Backbone Oxidation 面和经向pnn -钌螯合物在无碱丁腈水化中的协同配体主氧化

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-20 DOI: 10.1021/acs.inorgchem.5c03183

Gazal Sabharwal, Khilesh C. Dwivedi, Maravanji S. Balakrishna

{"title":"Facial and Meridional PNN-Ruthenium Pincer Complexes in Base-Free Nitrile Hydration with Concurrent Ligand Backbone Oxidation","authors":"Gazal Sabharwal, Khilesh C. Dwivedi, Maravanji S. Balakrishna","doi":"10.1021/acs.inorgchem.5c03183","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03183","url":null,"abstract":"A tridentate amide-pyridine-monophosphine ligand, {(o-PPh2)C6H4C(O)N(H)CH2(C5H4N)} (1), has been employed to synthesize a series of RuII and RuIII pincer complexes. Reaction of ligand 1 with [RuCl2(DMSO)4] and [RuCl2(PPh3)3] yielded [RuCl(C12H8N2){(PNN)-κ3-P,N,N}] (2) and [RuCl2(PPh3){(PNN)-κ3-P,N,N}] (3), respectively, while treatment with [RuHCl(CO)(PPh3)3] under varied conditions afforded pincer-type complexes [RuCl(CO)(PPh3){(PNN)-κ3-P,N,N}] (4), [RuH(CO)(PPh3){(PNN)-κ3-P,N,N}] (5), and [Ru(Cl)2(CO){(PNN)-κ3-P,N,N}]Cl (6). Ligand 1 upon reaction with [Ru(p-cymene)Cl2]2 and [RuCl2(PPh3)3] under aerobic reaction conditions afforded [RuCl(CH3CN)2{(o-PPh2)C6H4C(O)NC(O)(C5H4N)}-κ3-P,N,N] (7) and [RuCl2(CH3OH){(o-PPh2)C6H4C(O)NC(O)(C5H4N)}-κ3-P,N,N] (8) complexes, respectively, showing base- and additive-free benzylic C–H oxidation at room temperature. Complexes 4 and 5 were employed in the hydration of nitriles to amides. Mechanistic studies support a [Ru–H] active species facilitating water activation through a [Ru–H···H–OH] dihydrogen bond, enabling nucleophilic attack on the coordinated nitrile. The catalyst system operates at low loadings, tolerating both electron-rich and electron-deficient nitriles.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"88 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089386","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

Oxygen Evolution Reaction Driven by Plasmon-Induced Hot Holes and S-Scheme Synergy in CuS@Polypyrrole Nanorods. CuS@Polypyrrole纳米棒中等离子体诱导热洞驱动的析氧反应和s -方案协同作用。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-20 DOI: 10.1021/acs.inorgchem.5c03573

Zanling Huang,Jintao Zhang,Qian Hu,Yaoyao Chen,Weiwei Zhu,Abebe Reda Woldu,Liangsheng Hu

引用次数: 0

Luminescent Zn5-Based Covalent Metal-Organic Framework Showing ∼3.2 Å Pocket for Fluorescence Recognition and Determination of Ce(III). 发光基于zn5的共价金属-有机框架显示~ 3.2 Å口袋荧光识别和测定Ce（III）。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-19 DOI: 10.1021/acs.inorgchem.5c03672

Yi Tao Zhao,Xian Qing Xie,Le Le Gong,Rong Hua,Zhi Wu Yu,Feng Luo

引用次数: 0

Hydrogen Insertion Optimizes the Electronic State of Pd–Ir Nanoalloys to Enhance Methanol Electrocatalytic Oxidation 插入氢优化Pd-Ir纳米合金的电子态以增强甲醇电催化氧化。

IF 4.7 2区化学

Inorganic Chemistry Pub Date : 2025-09-19 DOI: 10.1021/acs.inorgchem.5c03656

Sizhuo Ma, , , Dan Huang, , , Jinjuan Zhao, , , Yuner Xu, , , Mengjie Li, , , Zheng Liu, , , Honglei Yang, , , Shuai Han*, , and , Shuwen Li*,

{"title":"Hydrogen Insertion Optimizes the Electronic State of Pd–Ir Nanoalloys to Enhance Methanol Electrocatalytic Oxidation","authors":"Sizhuo Ma, , , Dan Huang, , , Jinjuan Zhao, , , Yuner Xu, , , Mengjie Li, , , Zheng Liu, , , Honglei Yang, , , Shuai Han*, , and , Shuwen Li*, ","doi":"10.1021/acs.inorgchem.5c03656","DOIUrl":"10.1021/acs.inorgchem.5c03656","url":null,"abstract":"The optimized electronic state of an electrocatalyst is a powerful approach to promoting the methanol oxidation reaction (MOR). In this work, H incorporated into the Pd–Ir alloy decorated on nitrogen-doped graphene (designated as Pd7IrHx/NG) was fabricated through a mild method. As an electrocatalyst for MOR in alkaline media, Pd7IrHx/NG achieves a catalytic activity of 1625.0 mA mg–1 (mass activity) and 5.9 mA cm–2 (specific activity), along with exceptional long-term cycle stability. This far exceeds those of Pd7Ir/NG, PdHx/NG, Pd/NG, and commercial Pd/C catalysts. Structural characterization reveals that the electronic states of Pd and Ir in Pd7IrHx/NG in terms of binding energy and the ratio of zerovalent to oxidized metals were efficiently optimized through hydrogen insertion. Consequently, this modification creates more channels for the dual-coupled transfer of electrons and protons. This not only supplies an ample amount of active hydroxyl species but also optimizes the adsorption of intermediates. The results highlight the importance of optimizing the electronic state and provide an efficient strategy to design advanced electrocatalysts for small organic molecular electro-oxidation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 38","pages":"19497–19504"},"PeriodicalIF":4.7,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083612","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

Interaction of Congo Red with MOFs Facilitates Specific Detection of Cr(VI) in Water. 刚果红与mof的相互作用有助于水中Cr（VI）的特异性检测。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-19 DOI: 10.1021/acs.inorgchem.5c03177

Xu-Hui Zhao,Rui-Dong Wang,Jun-Fu Man,Zong-Qing Ma,Lei Wang,Wei-Ming Wei,Hua Liu,Wen-Qian Zhang,Lin Du,Qi-Hua Zhao

引用次数: 0