Polyhedron最新文献_第4页

Antioxidant, anti-acetylcholinesterase, antimicrobial, and anticancer activities of Morin–Cu(II) hybrid Nanoflowers Morin-Cu （II）杂交纳米花的抗氧化、抗乙酰胆碱酯酶、抗菌和抗癌活性

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-01 DOI: 10.1016/j.poly.2025.117917

Metin Yıldırım , Burcu Somtürk Yilmaz , Mehmet Çimentepe , Adem Necip , Özden Dellal

In recent years, various nanostructures, including nanoflowers, have attracted attention due to their effective biomedical properties. In this study, M@hNFs were synthesized using morin as the organic component and Cu²⁺ ions as the inorganic component. The prepared nanoflowers were characterized by SEM, EDX, FTIR, and XRD analyses, and their biological activities were subsequently investigated, including anticancer effects against MCF-7 breast cancer cells, acetylcholinesterase (AChE) inhibitory activity, antioxidant capacity, antibacterial activity against Staphylococcus aureus, Enterococcus faecalis (E. faecalis), Pseudomonas aeruginosa, Escherichia coli, methicillin-resistant Staphylococcus aureus (MRSA), and multidrug-resistant Escherichia coli (MDR E. coli) using the broth microdilution method, as well as antibiofilm activity against MRSA and MDR E. coli. SEM analysis revealed that the synthesized M@hNFs exhibited a diameter of 24.69 μm. Antioxidant assays demonstrated IC₅₀ values of 131.3 μg/mL (DPPH) and 51.3 μg/mL (ABTS). The AChE inhibitory activity was confirmed with an IC₅₀ value of 72.2 ± 2.1 μg/mL. Furthermore, M@hNFs reduced the viability of MCF-7 cells to 56 % at 500 μg/mL. In antibacterial assays, the synthesized hNFs exhibited stronger activity compared with morin alone, showing the most potent effect against E. faecalis with a MIC value of 32 μg/mL. Importantly, the hNFs also demonstrated activity against resistant strains, inhibiting MRSA and MDR E. coli at 256 μg/mL. At 1024 μg/mL, M@Cu-hNFs inhibited biofilm formation by MRSA and MDR E. coli by 69.7 % and 66.3 %, respectively. Taken together, these findings indicate that the prepared M@hNFs possess multiple biomedical properties and hold significant potential for further studies and future biomedical applications.

近年来，包括纳米花在内的各种纳米结构因其有效的生物医学特性而备受关注。本研究以桑里素为有机组分，Cu2+离子为无机组分合成了M@hNFs。采用SEM、EDX、FTIR和XRD对制备的纳米花进行了表征，并对其生物活性进行了研究，包括对MCF-7乳腺癌细胞的抗癌作用、对乙酰胆碱酯酶（AChE）的抑制活性、抗氧化能力、对金黄色葡萄球菌、粪肠球菌（E. faecalis）、铜绿假单胞菌、大肠杆菌、耐甲氧西林金黄色葡萄球菌（MRSA）的抑菌活性。利用肉汤微量稀释法检测耐多药大肠杆菌（MDR E. coli），以及抗MRSA和MDR E. coli的抗菌膜活性。SEM分析表明，合成的M@hNFs的直径为24.69 μm。抗氧化试验显示IC₅₀值为131.3 μg/mL （DPPH）和51.3 μg/mL （ABTS）。证实了AChE的抑制活性，IC₅₀值为72.2±2.1 μg/mL。此外，M@hNFs在500 μg/mL时将MCF-7细胞的存活率降低至56%。在抗菌实验中，合成的hNFs比单独的桑苷具有更强的抑菌活性，对粪肠杆菌的抑制作用最强，MIC值为32 μg/mL。重要的是，hnf也显示出对耐药菌株的活性，在256 μg/mL的浓度下抑制MRSA和MDR大肠杆菌。在1024 μg/mL浓度下，M@Cu-hNFs对MRSA和MDR大肠杆菌形成生物膜的抑制作用分别为69.7%和66.3%。综上所述，这些发现表明制备的M@hNFs具有多种生物医学特性，具有进一步研究和未来生物医学应用的巨大潜力。

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引用次数: 0

A Keplerate type polyoxometalate-based ionic liquids as heterogeneous hybrid catalysts for efficient oxidation desulfurization using hydrogen peroxide under mild reaction conditions 以Keplerate型多金属氧酸盐为基础的离子液体作为多相杂化催化剂，在温和反应条件下对过氧化氢进行高效氧化脱硫

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-01 DOI: 10.1016/j.poly.2025.117913

Mostafa Riahi Farsani

A novel heterogeneous catalyst based on a Keplerate-type polyoxometalate and ionic liquid, W₇₂Fe₃₀-IL, was synthesized via anion exchange between the giant {W₇₂Fe₃₀} cluster and [3-aminoethyl-1-methylimidazolium]Br. The structure of this catalyst was confirmed by FT-IR, Raman, XRD, CHNS, XRF, ICP and thermogravimetric analyses. The resulting hybrid exhibited excellent catalytic performance in the oxidative desulfurization (ODS) of model sulfur-containing compounds, including dibenzothiophene (DBT), benzothiophene (BT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), using hydrogen peroxide as a green oxidant under mild conditions. Various reaction parameters—oxidant-to-substrate ratio, catalyst loading, temperature, acid promoter, and substrate type—were systematically studied. W₇₂Fe₃₀-IL achieved 99.5 % sulfur removal from DBT at 40 °C within 90 min with an optimal H₂O₂/DBT molar ratio of 4:1. The catalytic activity followed the order DBT > 4,6-DMDBT > BT, correlating with electronic density and steric hindrance around the sulfur atom. Moreover, the catalyst showed excellent reusability over five cycles with minimal activity loss. High structural stability was confirmed by XRD and FTIR, with the hot filtration test and ICP analyse indicating no leaching. This study highlights the potential of Keplerate-type POM-ILs as efficient, recyclable, and environmentally friendly catalysts for deep fuel desulfurization, offering a promising alternative to conventional hydrodesulfurization, which operates under harsher conditions.

以keplerate型多金属氧酸盐和离子液体W₇₂Fe₃₀-IL为原料，通过巨大的{W₇₂Fe₃₀}簇与[3-氨基乙基-1-甲基咪唑]Br之间的阴离子交换，合成了一种新型非均相催化剂W₇₂Fe₃₀-IL。通过FT-IR、Raman、XRD、CHNS、XRF、ICP和热重分析证实了催化剂的结构。该杂化物在温和条件下以过氧化氢为绿色氧化剂，对二苯并噻吩（DBT）、苯并噻吩（BT）和4,6-二甲基二苯并噻吩（4,6- dmdbt）等模型含硫化合物的氧化脱硫（ODS）表现出优异的催化性能。系统地研究了各种反应参数——氧化剂与底物比、催化剂负载、温度、酸促进剂和底物类型。W₇₂Fe₃₀-IL在40°C下90分钟内从DBT中脱除99.5%的硫，最佳H₂O₂/DBT摩尔比为4:1。催化活性为DBT >； 4,6- dmdbt >； BT，与硫原子周围的电子密度和位阻有关。此外，该催化剂在5次循环中表现出优异的可重复使用性，且活性损失最小。XRD和FTIR分析证实了该材料具有较高的结构稳定性，热过滤试验和ICP分析表明其无浸出。该研究强调了keplerate型pom - il作为高效、可回收、环保的深层燃料脱硫催化剂的潜力，为在恶劣条件下运行的传统加氢脱硫提供了一种有希望的替代方案。

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引用次数: 0

Catalytic oxidation pathways for biomass-derived aromatics from lignin 木质素生物质衍生芳烃的催化氧化途径

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-29 DOI: 10.1016/j.poly.2025.117911

Xinquan Li , Hao Zhang , Mahdi M. Abu-Omar

The selective oxidation of lignin into value-added aromatic compounds represents a promising strategy for biomass valorization and the advancement of sustainable chemical feedstocks. This review highlights recent developments in aerobic lignin oxidation methods over the past decade. A mechanistic understanding of bond activation, including CC and CO cleavage pathways, is examined through studies of both model lignin compounds and complex lignin polymers. The role of transition-metal catalysts is discussed in the context of maximizing activity and selectivity.

木质素选择性氧化为高附加值芳香族化合物是生物质增值和可持续化工原料发展的一个有前途的策略。本文综述了近十年来好氧木质素氧化方法的最新进展。通过模型木质素化合物和复杂木质素聚合物的研究，对键激活的机制理解，包括CC和CO裂解途径进行了研究。从活性和选择性最大化的角度讨论了过渡金属催化剂的作用。

引用次数: 0

Antimony(III) complexes of benzaldehyde thiosemicarbazones: Synthesis, structural analysis, and biological evaluation 苯甲醛硫代氨基脲类锑配合物：合成、结构分析和生物学评价

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-29 DOI: 10.1016/j.poly.2025.117912

Ibrahim I. Ozturk , Okan Ucar , Anita M. Grześkiewicz , Maciej Kubicki , Christina N. Banti , Sotiris K. Hadjikakou

This study reports the successful synthesis and detailed characterization of three novel antimony(III) complexes with the general formulas [SbL₄Cl₂]·L·Cl (1), [SbL₃Cl₃] (2), and [SbL₃Br₃] (3), where “L” denotes a thiosemicarbazone derivative containing a benzene moiety. The complexes were obtained in excellent yields and exhibited high stability in both solid and solution states. Comprehensive spectroscopic analyses and single-crystal X-ray diffraction confirmed the monodentate coordination of the neutral thiosemicarbazone ligands to the Sb(III) center via the sulfur donor atom. The biological evaluation indicated that the complexes display enhanced antiproliferative activity against HeLa cervical cancer cells compared to their free ligands, suggesting their potential as anticancer agents. Additionally, the complexes demonstrated appreciable antibacterial activity, particularly against E. coli and S. epidermidis, indicating their promise as antimicrobial agents. Overall, this research advances the understanding of antimony(III) thiosemicarbazone complexes and highlights their potential relevance in drug development.

本文报道了三种新型锑（III）配合物的成功合成和详细表征，其通式为[SbL4Cl2]·L·Cl (1), [SbL3Cl3](2)和[SbL3Br3](3)，其中“L”表示含有苯片段的硫代氨基脲衍生物。该配合物收率高，在固溶状态下均表现出较高的稳定性。综合光谱分析和单晶x射线衍射证实了中性硫代氨基脲配体通过硫给体原子与Sb（III）中心的单齿配位。生物学评价表明，与游离配体相比，复合物对HeLa宫颈癌细胞具有更强的抗增殖活性，提示其作为抗癌药物的潜力。此外，这些复合物显示出明显的抗菌活性，特别是对大肠杆菌和表皮葡萄球菌，表明它们作为抗菌药物的前景。总的来说，本研究促进了对锑（III）硫代氨基脲配合物的理解，并强调了它们在药物开发中的潜在相关性。

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引用次数: 0

Electronic structure and reactivity of mixed-ligand dinuclear RuIr, RuRh, and RuRu polyhydride-bridged complexes: A DFT-based investigation 混合配体双核RuIr、ruh和ruu多氢化物桥接配合物的电子结构和反应性：基于dft的研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-28 DOI: 10.1016/j.poly.2025.117909

Abdelatif Messaoudi

This study presents a comprehensive theoretical analysis of a series of bimetallic diruthenium complexes [Cp^‡Ru(μ-H)₃IrCp^⁎], [Cp^‡Ru(μ-H)₃RhCp^⁎], [Cp^‡Ru (μ-H)₃{Ru(p-cymene)}], [Cp^‡Ru(μ-H)₃{Ru(benzene)}] and [Cp^‡Ru(μ-H)₂(μ-Cl){Ru(p-cymene)}] (Cp* = C₅Me₅, Cp^‡ = C5^tBu₃H₂, p-cymene = CH₃C₆H₄CH(CH₃)₂)) (A1-A5), incorporating various metal centers (Ir, Rh) and ligands (hydrides, chloride, Cp*) using density functional theory (DFT) at the B3LYP level with LanL2DZ and def2-TZVP basis sets. The geometric structures, electronic configurations, molecular orbitals, global reactivity descriptors, electrostatic potentials, atomic charges, TDOS, UV–Vis absorption spectra, and nonlinear optical (NLO) properties were systematically investigated. Geometry optimizations reveal excellent agreement with experimental data, with def2-TZVP offering slightly improved accuracy in metal-ligand bond distances and angles. The HOMO-LUMO gap analysis and frontier molecular orbitals show that complexes A1 and A5 have the narrowest gaps, indicating higher reactivity, while A3 displays the highest electron delocalization and charge transfer capability. Reactivity descriptors position A2 as the most electrophilic species, with high electronegativity and electron affinity, whereas A3 acts as the best donor. Molecular electrostatic potential (MESP) maps show distinct charge distributions and identify nucleophilic and electrophilic regions, highlighting the strong influence of ligand identity. Charge analysis supports significant polarization effects, particularly in A5 due to the chloride ligand. UV–Vis spectral simulations predict strong absorption in the visible region for A5, with metal to ligand charge transfer (MLCT) and π → π* transitions, indicating potential in photonic applications. Furthermore, NLO property analysis reveals that A3-A5 exhibit substantial hyperpolarizabilities, suggesting their promise as materials for second-order NLO applications. Altogether, this work underscores the sensitivity of electronic and optical properties to ligand environment, metal type, and computational treatment, offering valuable guidance for the design of functional organometallic complexes in catalysis, optoelectronics, and molecular electronics.

本研究利用密度泛函数理论（DFT）在B3LYP水平上结合了各种金属中心（Ir, Rh）和配体（氢化物，cl *），在LanL2DZ和def2-TZVP基集上，对一系列双金属钌配合物[Cp‡Ru(μ-H)3IrCp], [Cp‡Ru(μ-H)3{Ru(p-cymene)}], [Cp‡Ru(μ-H)3{Ru（苯）}]和[Cp‡Ru(μ-H)2(μ-Cl){Ru(p-cymene)} (Cp* = C5Me5, Cp‡= C5tBu3H2, p-cymene = CH3C6H4CH(CH3)2) （b1 - a5）进行了全面的理论分析。系统地研究了材料的几何结构、电子构型、分子轨道、整体反应性描述符、静电势、原子电荷、TDOS、紫外-可见吸收光谱和非线性光学性质。几何优化显示与实验数据非常吻合，def2-TZVP提供了金属配体键距离和角度的精度略有提高。HOMO-LUMO间隙分析和前沿分子轨道表明，配合物A1和A5的间隙最窄，反应活性较高，而A3的电子离域和电荷转移能力最强。反应性描述符表明A2是最亲电的物质，具有较高的电负性和电子亲和性，而A3是最好的供体。分子静电势（MESP）图显示出明显的电荷分布，并识别出亲核和亲电区域，突出了配体同一性的强烈影响。电荷分析支持显著的极化效应，特别是在A5中由于氯配体。紫外可见光谱模拟预测了A5在可见光区的强吸收，具有金属到配体的电荷转移（MLCT）和π→π*跃迁，表明其在光子领域的应用潜力。此外，NLO性质分析表明，A3-A5具有显著的超极化性，表明它们有望成为二阶NLO应用的材料。总之，这项工作强调了电子和光学性质对配体环境，金属类型和计算处理的敏感性，为催化，光电子和分子电子学中功能有机金属配合物的设计提供了有价值的指导。

{"title":"Electronic structure and reactivity of mixed-ligand dinuclear RuIr, RuRh, and RuRu polyhydride-bridged complexes: A DFT-based investigation","authors":"Abdelatif Messaoudi","doi":"10.1016/j.poly.2025.117909","DOIUrl":"10.1016/j.poly.2025.117909","url":null,"abstract":"<div><div>This study presents a comprehensive theoretical analysis of a series of bimetallic diruthenium complexes [Cp‡Ru(μ-H)3IrCp⁎], [Cp‡Ru(μ-H)3RhCp⁎], [Cp‡Ru (μ-H)3{Ru(p-cymene)}], [Cp‡Ru(μ-H)3{Ru(benzene)}] and [Cp‡Ru(μ-H)2(μ-Cl){Ru(p-cymene)}] (Cp* = C5Me5, Cp‡ = C5tBu3H2, p-cymene = CH3C6H4CH(CH3)2)) (A1-A5), incorporating various metal centers (Ir, Rh) and ligands (hydrides, chloride, Cp*) using density functional theory (DFT) at the B3LYP level with LanL2DZ and def2-TZVP basis sets. The geometric structures, electronic configurations, molecular orbitals, global reactivity descriptors, electrostatic potentials, atomic charges, TDOS, UV–Vis absorption spectra, and nonlinear optical (NLO) properties were systematically investigated. Geometry optimizations reveal excellent agreement with experimental data, with def2-TZVP offering slightly improved accuracy in metal-ligand bond distances and angles. The HOMO-LUMO gap analysis and frontier molecular orbitals show that complexes A1 and A5 have the narrowest gaps, indicating higher reactivity, while A3 displays the highest electron delocalization and charge transfer capability. Reactivity descriptors position A2 as the most electrophilic species, with high electronegativity and electron affinity, whereas A3 acts as the best donor. Molecular electrostatic potential (MESP) maps show distinct charge distributions and identify nucleophilic and electrophilic regions, highlighting the strong influence of ligand identity. Charge analysis supports significant polarization effects, particularly in A5 due to the chloride ligand. UV–Vis spectral simulations predict strong absorption in the visible region for A5, with metal to ligand charge transfer (MLCT) and π → π* transitions, indicating potential in photonic applications. Furthermore, NLO property analysis reveals that A3-A5 exhibit substantial hyperpolarizabilities, suggesting their promise as materials for second-order NLO applications. Altogether, this work underscores the sensitivity of electronic and optical properties to ligand environment, metal type, and computational treatment, offering valuable guidance for the design of functional organometallic complexes in catalysis, optoelectronics, and molecular electronics.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117909"},"PeriodicalIF":2.6,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145652072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Opposing effects of bipyridine ligand substitution on the luminescence of Sm(III) (f-f) and Ce(III) (d-f) complexes 联吡啶配体取代对Sm(III) （f-f）和Ce(III) （d-f）配合物发光的相反影响

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-28 DOI: 10.1016/j.poly.2025.117905

Qing-Dou Xu , Yu-Jing Ma , Han Xiao , Qian-Qian Yang , Min Cao , Jun-Jie Xu

To investigate the influence of the electron donating ability of the sensitization ligand on the photoluminescence properties in Sm(III) and Ce(III) complexes, a group of complexes [Sm(NO₃)₃(4,4′-dmbpy)₂] (1) and [Ce(NO₃)₃(4,4′-dmbpy)₂] (2) (4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized and fully characterized. Comparing the photoluminescence properties of complexes 1 and [Sm(NO₃)₃(bpy)₂] or 2 and [Ce(NO₃)₃(bpy)₂], the experimental results show that for Sm(III) complexes, decreasing the electron donating ability of the sensitization ligand leads to an increase in the maximum emission band intensity and fluorescence lifetime; for Ce(III) complexes, weakening the electron donating ability of the sensitization ligand results in a decrease in the maximum emission band intensity and fluorescence lifetime.

为了研究敏化配体的给电子能力对Sm（III）和Ce（III）配合物的光致发光性能的影响，合成了一组配合物[Sm(NO3)3(4,4 ' -dmbpy)2](1)和[Ce(NO3)3(4,4 ' -dmbpy)2] (2) （4,4 ' -dmbpy = 4,4 ' -二甲基-2,2 ' -联吡啶）。对比配合物1与[Sm(NO3)3(bpy)2]或2与[Ce(NO3)3(bpy)2]的光致发光性能，实验结果表明：对于Sm（III）配合物，敏化配体给电子能力的降低导致最大发射带强度和荧光寿命的增加；对于Ce（III）配合物，敏化配体给电子能力的减弱导致最大发射带强度和荧光寿命的降低。

引用次数: 0

Exploration of structural, magnetic, electrical polarization, optical and microwave absorption properties of rGO/hexaferrites composites 氧化石墨烯/六铁氧体复合材料的结构、磁性、电极化、光学和微波吸收性能的探索

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-27 DOI: 10.1016/j.poly.2025.117914

Mehboob Ali , Saba Sharif , Farhan Sadiq , Humaira Aslam , Zainab Altaf , Sadaf Naz , Imran Sadiq , Eman.A. Alghamdi , Muhammad Raheel , Muhammad Shahbaz , Saira Riaz , Shahzad Naseem

This study proposed the formation of rGO/Sr₂Fe₈O₁₄ nanocomposite for structural, magnetic, optical and microwave absorption applications. The reduced graphene oxide (rGO) and Strontium-based T-type hexaferrite (Sr₂Fe₈O₁₄) nanocomposites were prepared by ceramic method while the T-type hexaferrite was prepared by following the sol gel auto-combustion method. Respectively. The XRD analysis of all the samples confirmed the presence of both phases in the composites. The vibrating sample magnetometer (VSM) revealed that all the samples possessed a soft magnetic nature. The saturation and remanence magnetization increased while coercivity declined by enhancing T-type hexaferrite concentration in rGO. The polarization versus electric field hysteresis loops demonstrated the lossy behavior and this behavior increased with the addition of T-type hexagonal ferrites. To analyze the optical investigation, photo-luminance (PL) and UV–visible spectroscopies were employed. The PL outcomes revealed the ultraviolet and visible region emission. The UV–visible spectroscopy results showed the enhancement in absorbance of photo-energy with the addition of T-type content while optical band gap energy decreased. The pure T-type hexaferrites sample exhibited the maximum value of microwave absorption (−23.04) at 0.46 GHz frequency. These results divulge the importance of the present synthesized composites in photo-catalytic activities and microwave absorption properties.

本研究提出了rGO/Sr2Fe8O14纳米复合材料在结构、磁性、光学和微波吸收等方面的应用。采用陶瓷法制备了还原氧化石墨烯（rGO）和锶基t型六铁体（Sr2Fe8O14）纳米复合材料，采用溶胶-凝胶自燃烧法制备了t型六铁体。分别。所有样品的XRD分析证实了复合材料中两相的存在。振动样品磁强计（VSM）显示，所有样品都具有软磁性质。提高氧化石墨烯中t型六铁氧体的浓度，可以提高饱和磁化强度和剩磁强度，降低矫顽力。极化-电场磁滞回线表现出损耗行为，并随着t型六方铁氧体的加入而增强。采用光度法和紫外可见光谱法对其进行光学分析。PL结果显示紫外区和可见光区发射。紫外可见光谱结果表明，随着t型含量的增加，光能的吸光度增强，光带隙能降低。纯t型六铁氧体样品在0.46 GHz频率处的微波吸收最大值为- 23.04。这些结果揭示了所合成的复合材料在光催化活性和微波吸收性能方面的重要性。

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引用次数: 0

Functional MOFs anode protection layer design for high-performance aqueous zinc ion batteries 高性能锌离子水电池功能MOFs阳极保护层设计

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-27 DOI: 10.1016/j.poly.2025.117915

Xunfei Ma , Bo Sun , Xiaochen Liu , Han Yu , Na Sun , Zhe Gong , Mingdong Zhou , Yaguang Sun

The electrochemical performance of aqueous zinc-ion batteries (ZIBs) is significantly hindered by dendritic growth of the zinc anode, which shortens the cycling life. To address these challenges, a two-dimensional (2D) zinc-based metal-organic framework (MOF), namely a Zn(II) coordination polymer (ZHPCA) [1], was synthesized via a solvothermal method. The ZCu-modified zinc electrode (ZCu@Zn) was fabricated by integrating ZHPCA with copper powder as an interfacial modification layer (ZCu), using carboxymethyl cellulose (CMC) as a binder. The ZCu layer effectively mitigated both the hydrogen evolution reaction (HER) and surface corrosion of the zinc anode. During the zinc deposition/stripping process, ZCu provided an effective substrate for zinc-ion nucleation, enabling uniform deposition and structural homogenization, thereby effectively suppressing dendrite growth. As a result, the assembled ZCu@Zn||ZCu@Zn symmetric battery demonstrated a low over potential of 40 mV and an extended cycle life of 900 h. In addition, activated carbon (AC) was employed as the cathode to assemble ZCu@Zn||AC hybrid capacitors, which exhibited a significantly enhanced capacitive performance. In conclusion, employing ZCu@Zn as a modified zinc anode offers a promising strategy for improving the stability and reversibility of aqueous zinc-ion batteries.

锌阳极的枝晶生长严重影响了水基锌离子电池的电化学性能，缩短了电池的循环寿命。为了解决这些挑战，通过溶剂热法合成了一种二维（2D）锌基金属有机骨架（MOF），即Zn（II）配位聚合物（ZHPCA）[1]。以羧甲基纤维素（CMC）为粘结剂，将ZHPCA与铜粉作为界面改性层（ZCu）相结合，制备了ZCu修饰锌电极（ZCu@Zn）。ZCu层有效地减轻了析氢反应（HER）和锌阳极的表面腐蚀。在锌沉积/剥离过程中，ZCu为锌离子成核提供了有效的衬底，实现了均匀沉积和结构均匀化，从而有效抑制了枝晶的生长。结果表明，组装的ZCu@Zn||ZCu@Zn对称电池的过电位低至40 mV，循环寿命延长至900 h。此外，采用活性炭（AC）作为阴极组装ZCu@Zn||交流混合电容器，其电容性能得到了显著提高。综上所述，采用ZCu@Zn作为锌阳极的改性，为提高锌离子电池的稳定性和可逆性提供了一种很有前途的策略。

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引用次数: 0

Synthesis and structural characterization of self-assembled silver(I) complexes of the pyrazole ligands: effect of anion and VT NMR study 吡唑配体自组装银配合物的合成与结构表征：阴离子效应与VT NMR研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-24 DOI: 10.1016/j.poly.2025.117910

Munmun Mondal, Ganesan Mani

The effect of an anion on the structure of the silver complex is investigated. The reaction between 2-(3,5-dimethylpyrazolylmethyl)-5-(phenylsulfonylmethyl)pyrrole LH and AgBF₄ gives a discrete two-coordinate silver complex [Ag(LH)₂]BF₄ 1. Conversely, the same ligand LH reacts with AgOCOCF₃ to give an extended 1D polymeric network structure [Ag(μ-LH)(μ-CF₃COO)]_n 2. With a silver ion containing the divalent sulfate ion, it forms a three-coordinate silver complex [Ag(LH)₃]₂SO₄ 3, which encapsulates the SO₄²⁻ ion in its cavity. Yet another polymeric structure that encapsulates SO₄²⁻ ion [Ag₂(3,5-dimethylpyrazole)₄(μ-SO₄)] 4 was obtained by treating Ag₂SO₄ with 3,5-dimethylpyrazole. Complex 4 exhibits a dynamic behavior in solution between the sulfate-bridged complexes with the trans and cis orientations of the pyrazole NH groups, as studied by the variable temperature (VT) ¹H NMR method. The important features are the argentophilic interaction, the pyrrole ring π-interaction, and the ditopic nature of ligands LH and 3,5-dimethylpyrazole, which all facilitate the formation of these structurally intriguing complexes.

研究了阴离子对银配合物结构的影响。2-（3,5-二甲基吡唑甲基）-5-（苯基磺酰基甲基）吡咯LH与AgBF4反应得到离散的双配位银配合物[Ag(LH)2] bf41。相反，相同的配体LH与AgOCOCF3反应得到扩展的一维聚合物网络结构[Ag(μ-LH)(μ-CF3COO)]n 2。它与含有二价硫酸盐离子的银离子形成三配位银配合物[Ag(LH)3]2SO4 3，将SO42−离子包裹在其腔内。用3,5-二甲基吡唑处理Ag2SO4，得到了另一种包封SO42−离子[Ag2（3,5-二甲基吡唑）4(μ-SO4)] 4的聚合物结构。通过变温（VT） 1H NMR方法研究了配合物4在具有吡唑NH基团反式和顺式取向的硫酸盐桥接配合物之间的溶液动力学行为。重要的特征是亲阿根廷相互作用，吡咯环π相互作用，以及配体LH和3,5-二甲基吡唑的异位性，这些都有助于形成这些结构有趣的配合物。

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引用次数: 0

Nitromethane gas absorption in interlocked icosahedral M12L8 nanocages 互锁二十面体M12L8纳米笼对硝基甲烷气体的吸收

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-24 DOI: 10.1016/j.poly.2025.117908

Stefano Elli, Antonino Famulari, Javier Martí-Rujas

The self-assembly of tris-pyridyl-benzene ligand with ZnI₂ in the presence of benzaldehyde yields a poly-[n]-catenane formed of large M₁₂L₈ metal organic cages (MOCs) which is used to study guest exchange of small non-aromatic molecules like nitromethane. X-ray crystallographic analysis revealed that guest exchange reaction takes place via gas-solid single-crystal-to-single-crystal (SCSC) process. The single crystal X-ray diffraction (SC-XRD) data allowed to determine the ordered guest content within the M₁₂L₈ nanocages. Density Functional Theory (DFT) calculations specific for solid state crystalline systems have been carried out to estimate the energy interactions among host and guest molecules (E_host-guest) and to compute the maps of electrostatic potential (MEPs) for each guest. The outcomes of the DFT results helped to rationalize the guest exchange reaction considering both ordered and disordered molecules in the system were the E_host-guest differs only in ∼4 kcal/mol. The role of the interlocking among M₁₂L₈ cages in the host dynamic behavior and the overall catenane structural stability is emphasised. The observed nitromethane guest uptake is important in the field of gas-solid molecular inclusion for instance in applications for the absorption of gases like CO₂, CH₄, SO₂ or NOx compounds.

在苯甲醛存在下，三吡啶苯配体与ni - 2自组装生成由M12L8金属有机笼（MOCs）组成的聚[n]-catenane，用于硝基甲烷等非芳香族小分子的客体交换研究。x射线晶体学分析表明，客体交换反应是通过气固单晶到单晶（SCSC）过程发生的。单晶x射线衍射（SC-XRD）数据可以确定M12L8纳米笼内有序客体的含量。密度泛函理论（DFT）计算特定于固态晶体系统进行估计宿主和客体分子（主客体）之间的能量相互作用，并计算静电势（MEPs）图为每个客体。DFT结果有助于使客体交换反应合理化，考虑到系统中有序分子和无序分子的差异仅为4 kcal/mol。强调了M12L8笼间互锁在宿主动态行为和整体链烷结构稳定性中的作用。观察到的硝基甲烷客体吸收在气固分子包裹体领域非常重要，例如在吸收CO2、CH4、SO2或NOx化合物等气体的应用中。

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引用次数: 0