Polyhedron最新文献_第9页

Nano-composites of rare earth cerium metal doped cobalt ferrites with conducting polymers for hybrid supercapacitors 杂化超级电容器用稀土铈金属掺杂钴铁氧体与导电聚合物纳米复合材料

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-12 DOI: 10.1016/j.poly.2025.117874

Muhammad Waheed Mushtaq , Muhammad Shahbaz , Farah Kanwal , Areeba Khursheed , Asma Ahmad , Shahzad Sharif , Zeeshan Mustafa , Shahid Bashir , Kainat Ali

Cobalt ferrites (CF) nanoparticles were synthesized by hydrothermal method. Cerium doping as well as incorporation of conductive polymers like polypyrrole (PPy) and polyaniline (PANI) via in situ polymerization were carried out to enhance electrochemical performance. Structural characterization was performed using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM), dynamic light scattering (DLS) and transmission electron microscope (TEM). Electrochemical attributes of synthesized materials were divulged in three-electrode set up with 1 M KOH electrolyte. CF displayed specific capacity of 62 C/g which was improved to 83.3 C/g by doping with cerium. Use of conductive polymer unlocked the extraordinary potential of cerium doped CF exhibiting specific capacity of 90 C/g and 130.6 C/g for CeCF-2@PANI and CeCF-2@PPy. Practical applications of CeCF-2@PPy were also authenticated by fabricating it against activated carbon (AC) forming hybrid supercapacitor which showed specific capacity of 67.98 C/g with specific energy of 13.5 Wh/kg and specific power of 993.3 W/kg at 1 A/g. The stability test was performed by running the device for 5000 GCD cycles which exhibited 99 % coulombic efficiency. Such marvelous properties of the nanocomposite are attributed to cerium doping incorporated with PPy which can serve as a torch bearer for the enthusiastic researchers to implement the idea on novel materials to design efficient electrode materials for futuristic energy storage devices.

采用水热法制备了钴铁氧体纳米颗粒。为了提高电化学性能，采用原位聚合的方法掺杂铈以及加入聚吡咯（PPy）和聚苯胺（PANI）等导电聚合物。采用傅里叶变换红外（FTIR）光谱、x射线衍射（XRD）、原子力显微镜（AFM）、动态光散射（DLS）和透射电子显微镜（TEM）对结构进行了表征。在1 M KOH电解液的三电极条件下，揭示了合成材料的电化学特性。CF的比容量为62 C/g，掺铈后比容量达到83.3 C/g。使用导电聚合物释放了铈掺杂CF的非凡潜力，其CeCF-2@PANI和CeCF-2@PPy的比容量分别为90 C/g和130.6 C/g。通过活性炭（AC）复合超级电容器的制备，验证了CeCF-2@PPy的实际应用。该复合超级电容器在1 A/g下的比容量为67.98 C/g，比能量为13.5 Wh/kg，比功率为993.3 W/kg。稳定性试验表明，该装置运行5000 GCD循环，库仑效率达到99%。这种纳米复合材料的优异性能归功于掺杂了铈的PPy，它可以作为火炬手，为热心的研究人员实现新材料的想法，为未来的储能设备设计高效的电极材料。

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引用次数: 0

Synthesis and characterization of dichloro-η2-nitratobis(triphenylphosphine)iridium(III) 二氯-η -硝基（三苯基膦）铱（III）的合成与表征

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-12 DOI: 10.1016/j.poly.2025.117885

Dennis Awasabisah , Jack F. Gangemi , Nobuyuki Yamamoto

The iridium(III) nitrato complex, IrCl₂(η²-O₂NO)(PPh₃)₂ has been prepared from the air exposure of a CH₂Cl₂ solution of IrCl₃(n-BuONO)(PPh₃)₂, which is an adduct generated when IrCl₃(PPh₃)₂ is treated with n-BuONO. Both complexes IrCl₂(η²-O₂NO)(PPh₃)₂ and IrCl₃(n- BuONO)(PPh₃)₂ have been characterized by IR, ¹H NMR, ³¹P NMR, mass spectrometry, and elemental analysis. The X-ray crystal structure of IrCl₂(η²-O₂NO)(PPh₃)₂ reveals a pseudo-octahedral complex with the nitrato ligand bound to Ir in a bidentate fashion. The IrCl₂(η²-O₂NO)(PPh₃)₂ complex is air-stable as solid, but reacts with CO and NO in CH₂Cl₂ solution to produce IrCl₂(CO)(η¹-ONO₂)(PPh₃)₂ and IrCl₂(NO)(η¹-ONO₂)(PPh₃)₂, respectively as evidenced by MS and IR spectral data. Cyclic voltammetry and DFT calculations of the frontier molecular orbitals (FMO) of IrCl₂(η²-ONO₂)(PPh₃)₂ suggest reduction occurs at the nitrato region, while reduction of IrCl₃(n-BuONO)(PPh₃)₂ occurs in the vicinity of the IrN(=O) − OR moiety. Additionally, the DFT calculations support the spectroscopic data and the electrochemical behaviors of the complexes.

IrCl3(n-BuONO)(PPh3)2是IrCl3(PPh3)2经n-BuONO处理后生成的加合物，经CH2Cl2溶液暴露于空气中制备了IrCl2(η2-O2NO)(PPh3)2硝酸铱配合物。配合物IrCl2(η2-O2NO)(PPh3)2和IrCl3(n- BuONO)(PPh3)2通过IR、1H NMR、31P NMR、质谱和元素分析进行了表征。IrCl2(η2-O2NO)(PPh3)2的x射线晶体结构显示出一个伪八面体配合物，硝酸配体以双齿方式与Ir结合。质谱和红外光谱数据表明，IrCl2(η - 2- o2no)(PPh3)2配合物在固体状态下空气稳定，但在CH2Cl2溶液中与CO和NO反应生成IrCl2(CO)(η - 1- ono2)(PPh3)2和IrCl2(NO)(η - 1- ono2)(PPh3)2。IrCl2(η - 2- ono2)(PPh3)2的前沿分子轨道（FMO）的循环伏安法和DFT计算表明，还原发生在硝基区，而IrCl3(n-BuONO)(PPh3)2的还原发生在IrN(=O)−OR部分附近。此外，DFT计算支持光谱数据和配合物的电化学行为。

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引用次数: 0

First-principles investigation of the structural, electronic, optical, mechanical, and elastic anisotropy of halide double perovskites K₂AlAgX₆ (X = Cl, Br, I) for advanced energy applications 卤化物双钙钛矿K₂AlAgX₆（X = Cl, Br， I）的结构、电子、光学、机械和弹性各向异性的第一性原理研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-09 DOI: 10.1016/j.poly.2025.117877

Muhammad Mudassir Ahmad Alwi , Muhammad Jawad , Akbar niaz butt , Noor ul Amin

This study presents a comprehensive first-principles investigation of halide double perovskites K₂AlAgX₆ (X = Cl, Br, I) using density functional theory. The structural stability of the compounds is confirmed through optimized geometry, tolerance factor, and formation energy analysis. Electronic band structure calculations reveal indirect band gaps, which decrease from K₂AlAgCl₆ to K₂AlAgI₆, indicating enhanced visible-light absorption for iodide-based systems. Optical properties such as the dielectric function, refractive index, absorption coefficient, and reflectivity are evaluated, confirming strong photon interaction in the visible to ultraviolet region. Mechanical analysis based on the elastic constants demonstrates mechanical stability and ductile behavior. Furthermore, anisotropy in Young's modulus, Poisson's ratio, shear modulus, and linear compressibility is visualized using ELATE-generated 2D and 3D plots. These findings suggest that K₂AlAgX₆ perovskites are promising candidates for optoelectronic and energy-related applications due to their tunable band gaps, strong light-matter interaction, and favorable mechanical properties.

利用密度泛函理论对卤化物双钙钛矿K₂AlAgX₆（X = Cl, Br， I）进行了第一性原理研究。通过优化的几何形状、容差系数和地层能量分析，确定了化合物的结构稳定性。电子能带结构计算表明，从K₂AlAgCl₆到K₂AlAgI₆的间接能带间隙减小，表明含碘体系对可见光的吸收增强。光学性质，如介电函数，折射率，吸收系数和反射率进行了评估，确认强光子相互作用在可见到紫外区域。基于弹性常数的力学分析证明了其力学稳定性和延性。此外，杨氏模量、泊松比、剪切模量和线性压缩率的各向异性使用elate生成的2D和3D图进行可视化。这些发现表明，K₂AlAgX₆钙钛矿由于其可调的带隙、强的光-物质相互作用和良好的机械性能，是光电和能源相关应用的有希望的候选者。

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引用次数: 0

Design of an NNO-based fluorogenic chemosensor for Hg2+ ion detection: Structural characterization and biological imaging in cells and zebrafish 用于Hg2+离子检测的基于nno的荧光化学传感器的设计：细胞和斑马鱼的结构表征和生物成像

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-09 DOI: 10.1016/j.poly.2025.117873

Deboshmita Mukherjee , Dilip Sarkar , Rahul Kumar Singh , Md. Bakibillah , Arpita Das , Anoop Kumar , Rambabu Dandela , Samudra Gupta , Subhra Prakash Hui , Rajesh Kumar Das

A novel fluorescent chemosensor, designated as L, was synthesized for the detection of Hg²⁺ ions through the reaction of 2-methoxy-5-methyl aniline with pyridine-2-carboxaldehyde. The presence of Hg²⁺ resulted in a significant reduction in fluorescence. This sensor demonstrated the ability to quantify Hg²⁺ in aqueous samples at a pH of 4.4, and in vitro experiments with A549 cells exhibited fluorescence in the presence of Hg²⁺.The detection limit for chemosensor L was determined to be 0.392 μM, indicating its potential as a highly sensitive detector for Hg²⁺. Additionally, we successfully obtained single crystals of the HgCl₂L complex and characterized it using various spectroscopic techniques e.g., FT- IR, UV- Vis and SCXRD. Various significant stretching frequencies corresponding to C(H) = N, CO of methoxy group as well as (Hg − N) + (Hg − O) bonds are observed in FT- IR spectra, whereas the UV- Visible spectra clearly shows some intense absorption bands regarding ILCT. A series of experiments were conducted to detect Hg²⁺ in living cells and embryonic zebrafish using chemosensor L.

通过2-甲氧基-5-甲基苯胺与吡啶-2-甲醛的反应，合成了一种用于检测Hg2+离子的新型荧光化学传感器L。Hg2+的存在导致荧光显著降低。该传感器能够定量测定pH为4.4的水溶液中的Hg2+，并在A549细胞的体外实验中显示出Hg2+存在的荧光。化学传感器L的检出限为0.392 μM，具有作为Hg2+高灵敏度检测器的潜力。此外，我们成功地获得了HgCl2L配合物的单晶，并使用FT- IR， UV- Vis和SCXRD等多种光谱技术对其进行了表征。在FT- IR光谱中观察到C(H) = N、甲氧基CO和(Hg−N) + (Hg−O)键对应的各种显著的拉伸频率，而紫外-可见光谱则清晰地显示出ILCT的一些强吸收带。利用化学传感器L对活细胞和胚胎斑马鱼体内的Hg2+进行了检测。

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引用次数: 0

The significant role of cerium, gallium, and zirconium in cu-based catalyst for syngas to methanol: a bench scale experimental approach 铈、镓和锆在合成气制甲醇的铜基催化剂中的重要作用：一个实验规模的方法

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-08 DOI: 10.1016/j.poly.2025.117875

Shiva Kumar Saw , Sudipta Datta , Pavan K. Gupta , Binod Kumar , Prakash D. Chavan , Shweta Kumari , Gajanan Sahu , Nilesh D. Dhaigude

The Cu-based catalysts mainly accounted for the synthesis of methanol from synthesis gas. The promotion of Cu-based catalysts resulted in a significant increase in methanol selectivity, even with small quantities of an effective promoter. The CuZn system without promoter and with promoters such as Cerium (Ce), Gallium (Ga), and Zirconium (Zr) are induced in the CuZn system individually and studied their ease of Cu reduction. All four catalysts have been prepared via the coprecipitation method, and an experimental study has been carried out for syngas hydrogenation to methanol on a bench-scale fixed bed tubular reactor at 60 bar and 200 °C. The synthesized catalysts were characterized by multiple techniques, including Field Emission Scanning Electron Microscopy (FE-SAM), and Energy Dispersive X-ray Spectroscopy (EDS), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Temperature programmed reduction (TPR), Brunauer–Emmett–Teller (BET) surface area analyzer, X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), True Density-Porosity, Thermogravimetric Analysis (TGA), and the liquid product has been studied by Gas chromatography-FID and Karl fisher titrator. The determinantal effect of Ce, Ga, and Zr doping in the CuZn catalyst and their respective activity has been studied based on electronic, geometric, reaction kinetics, and acid/base surface properties. This paper has briefly deliberated on the syngas, mainly CO hydrogenation to methanol over each of the catalysts for 72 h as well as the space-time yield (STY) and methanol selectivity. The cause of significant improvements in activity and stability regarding STY of Ce-promoted CuZn catalyst over Ga and Zr promoted on the CuZn system has been elaborated. The Influence of Ce, Ga & Zr for higher active Cu dispersion on the catalyst surface to promote its activity towards methanol synthesis has been briefly annotated.

铜基催化剂主要用于合成气合成甲醇。促进铜基催化剂导致甲醇选择性显著增加，即使少量有效的促进剂。分别在CuZn体系中诱导无启动子和有启动子铈（Ce）、镓（Ga）和锆（Zr）的CuZn体系，并研究了它们对Cu的还原性。采用共沉淀法制备了四种催化剂，并在60 bar、200℃的固定床管式反应器上进行了合成气加氢制甲醇的实验研究。采用场发射扫描电镜（FE-SAM）、能量色散x射线能谱（EDS）、x射线衍射（XRD）、x射线光电子能谱（XPS）、程序升温还原（TPR）、布鲁诺尔-埃米特-泰勒（BET）表面积分析仪、x射线荧光（XRF）、傅里叶变换红外光谱（FTIR）、真密度-孔隙度、热重分析（TGA）、用气相色谱- fid和卡尔费雪滴定仪对液相产物进行了研究。基于电子、几何、反应动力学和酸碱表面性质，研究了Ce、Ga和Zr掺杂对CuZn催化剂及其各自活性的决定作用。本文简要讨论了合成气，主要是CO在每种催化剂上加氢72 h制甲醇，以及时空产率（STY）和甲醇选择性。阐述了ce促进CuZn催化剂的活性和稳定性比Ga和Zr促进CuZn催化剂的活性和稳定性显著提高的原因。简要说明了Ce、Ga和Zr对催化剂表面高活性Cu分散的影响，从而提高了催化剂合成甲醇的活性。

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引用次数: 0

A computational and machine learning-driven investigation of Ca3BiBr3 perovskite solar cells: Fine-tuning the hole transport layer for enhanced performance Ca3BiBr3钙钛矿太阳能电池的计算和机器学习驱动研究：微调空穴传输层以提高性能

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-05 DOI: 10.1016/j.poly.2025.117871

Bipul Chandra Biswas , Asadul Islam Shimul , Mohd Shkir , Farhat S. Khan , Mohamed Benghanem , R. Marnadu , Md. Azizur Rahman

Ca₃BiBr₃ is a promising candidate for solar cell applications due to its exceptional optical and electrical properties. Its absorptive properties have the capability to improve efficiency and minimize production costs in solar energy systems. To examine the optoelectronic characteristics and determine the most effective structure for improved performance, this investigation implements extensive simulations utilizing SCAPS-1D and DFT tools. DFT computations reveal that Ca₃BiBr₃ has a direct bandgap of 1.491 eV, accompanied by excellent absorption coefficients and exceptional structural stability, underscoring its promise as an effective material for solar applications. The device structure that has been evaluated using SCAPS-1D is composed of Ag/FTO/ETL/Ca₃BiBr₃/HTL/Ni, which includes a single electron transport layer (ETL) and multiple hole transport layers (HTLs). The device's efficacy was enhanced by optimizing critical parameters, such as thickness, temperature, doping concentration, defect density, and series-shunt resistances. The configuration of Ag/FTO/ZnO/Ca₃BiBr₃/CBTS/ Ni displayed the highest power conversion efficiency (PCE) of 28.57 %, an open-circuit voltage (V_OC) of 1.154 V, a short-circuit current density (J_SC) of 27.964 mA/cm², and a fill factor (FF) of 88.52 %. This optimized design outperformed devices with alternative HTLs, including CuO, CFTS, Spiro-OMeTAD, CuI, and CBTS. The significance of precise material and structural optimization in enhancing the efficacy of perovskite solar cells (PSCs) is underscored by this study. To improve interpretability, machine learning-based Random Forest algorithms were adopted to analyze the influence of critical factors on device performance. The results highlight that the characteristics of the resistance and absorber layers are crucial in influencing total efficiency. The integration of machine learning with conventional simulation methods establishes a strong foundation for the advancement of scalable, efficient PV technologies.

Ca3BiBr3由于其优异的光学和电学性能而成为太阳能电池应用的有前途的候选者。它的吸收特性能够提高太阳能系统的效率和降低生产成本。为了研究光电特性并确定最有效的结构以提高性能，本研究利用SCAPS-1D和DFT工具进行了广泛的模拟。DFT计算表明，Ca3BiBr3具有1.491 eV的直接带隙，具有优异的吸收系数和优异的结构稳定性，强调了其作为太阳能应用的有效材料的前景。利用SCAPS-1D评价的器件结构由Ag/FTO/ETL/Ca3BiBr3/HTL/Ni组成，其中包括单个电子传输层（ETL）和多个空穴传输层（HTLs）。通过优化关键参数，如厚度、温度、掺杂浓度、缺陷密度和串联并联电阻，提高了器件的效率。Ag/FTO/ZnO/Ca3BiBr3/CBTS/ Ni结构的最高功率转换效率（PCE）为28.57%，开路电压（VOC）为1.154 V，短路电流密度（JSC）为27.964 mA/cm2，填充因子（FF）为88.52%。这种优化的设计优于使用其他html的设备，包括CuO， CFTS, Spiro-OMeTAD， CuI和CBTS。本研究强调了精确的材料和结构优化对提高钙钛矿太阳能电池（PSCs）效能的重要性。为了提高可解释性，采用基于机器学习的随机森林算法分析关键因素对设备性能的影响。结果表明，电阻层和吸收层的特性对总效率的影响至关重要。机器学习与传统仿真方法的集成为可扩展、高效的光伏技术的发展奠定了坚实的基础。

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引用次数: 0

Current roles of metal-organic framework-based materials for the treatment of aquatic phenolic pollutants: detectors, adsorbents, and catalysts 金属有机骨架材料在水生酚类污染物处理中的作用：探测器、吸附剂和催化剂

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-05 DOI: 10.1016/j.poly.2025.117872

Qianzhe Zhang, Zehai Xu, Guoliang Zhang

Phenolic compounds are among the most harmful pollutants in industrial wastewater and they have long been regarded as notorious in water treatment because of their high toxicity and resistance to degradation. Metal-organic frameworks (MOFs) are highly promising for the removal of phenolic pollutants from water owing to their exceptional properties, including ultrahigh surface area, customizable porosity, well-defined crystallinity, and strong affinity for phenolic molecules. However, due to limitations of pristine MOFs (e.g., poor stability, slow response, and low selectivity), functional design of MOF-based materials is needed to improve their efficacy in the treatment of phenolic pollutants in water. In this review, we provide an in-depth analysis of the design and fabrication of MOF-based nanomaterials by combining MOFs with metals, oxidants, polymers, biomaterials, enzymes, and other components to enhance the performance of these engineered nano-tools in the treatment of aquatic phenolic pollutants. Among these designs, detectors are designed using MOF-based materials with excellent colorimetric/luminescent responses and outstanding electrochemical properties; Adsorbents are constructed from MOF-based composites that utilize synergistic effects including H-bonding, π-π interactions, electrostatic forces, and donor-acceptor effects for strong phenolic contaminant adsorption; catalysts are obtained through MOF hybrid nanostructures that can advantageously employ electro-/photocatalysis, catalytic reduction, and enzymatic pathways. These three categories of designed nano-tools pave a new pathway for MOF-based nanomaterials in industrial wastewater treatment of phenolic pollutants.

酚类化合物是工业废水中最有害的污染物之一，由于其高毒性和难降解性，长期以来在水处理中被认为是臭名昭著的。金属有机框架（mof）由于其特殊的性能，包括超高的表面积、可定制的孔隙度、明确的结晶度和对酚类分子的强亲和力，在去除水中酚类污染物方面非常有前途。然而，由于原始mof的局限性（稳定性差、响应慢、选择性低），需要对mof基材料进行功能设计，以提高其对水中酚类污染物的处理效果。在这篇综述中，我们深入分析了mof基纳米材料的设计和制造，通过将mof与金属、氧化剂、聚合物、生物材料、酶和其他成分结合，来提高这些工程纳米工具在处理水生酚类污染物方面的性能。在这些设计中，探测器采用mof基材料设计，具有优异的比色/发光响应和出色的电化学性能；吸附剂由mof基复合材料构成，利用协同效应，包括h键、π-π相互作用、静电力和供体-受体效应来吸附强酚类污染物；催化剂是通过MOF混合纳米结构获得的，这种结构有利于电/光催化、催化还原和酶促途径。这三类纳米工具的设计为mof基纳米材料在工业废水中处理酚类污染物开辟了新的途径。

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引用次数: 0

Synthesis, structure and magnetic properties of the monocapped 3d-metal(II) tris-N,S-heterocyclooximates: the design of cobalt pseudoclathrochelate with a single-ion magnet behavior 单包三维金属（II）三氮杂环肟酸盐的合成、结构和磁性：具有单离子磁性行为的钴假螯合物的设计

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-04 DOI: 10.1016/j.poly.2025.117860

Svetlana A. Belova , Alexander S. Belov , Ekaterina G. Lebed , Anastasia A. Danshina , Pavel V. Dorovatovskii , Artem S. Bogomyakov , Alexey I. Dmitriev , Mikhail V. Zhidkov , Denis V. Korchagin , Yan Z. Voloshin

Template condensation of 4-acetylthiazoloxime as a chelating ligand synthon and phenylboronic acid as a Lewis-acidic cross-linking agent on the nickel(II) ion using its perchlorate salt gave the ionic associate of phenylboron-monocapped nickel(II)-centered tris-thiazoloximate cation with ClO₄⁻ counter-anion. That with metal(II) chlorides (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Mn²⁺ and Zn²⁺) as the sources of M²⁺ ions afforded the corresponding chloride-H-bonded pseudomacrobicyclic intracomplexes. As follows from the single-crystal X-ray diffraction data, their pseudomacrobicyclic structures are formed by CH…Cl⁻ contacts with three N,S-heterocyclic groups of thiazoloximate synthons. Fe(II), Co(II) and Zn(II) ions are located in the centers of their trigonal-prismatic MN₆-coordination polyhedra, while geometry of NiN₆-polyhedra is intermediate between a trigonal prism and trigonal antiprism. All the prepared metal(II) pseudoclathrochelates were also characterized using elemental analysis, PXRD, MALDI-TOF MS, UV–vis and NMR methods. According to the magnetometry and X-ray diffraction data, their metal(II) ions are in high-spin states. The ac and dc magnetic studies, supported by the SA-CASSCF/NEVPT2 quantum chemical calculations, revealed that a given cobalt(II) pseudoclathrochelate exhibits the strong uniaxial magnetic anisotropy due to the unquenched angular orbital momentum. It also demonstrates a zero-field single-molecule magnet behavior with quantum tunneling of the magnetization as the only one magnetically sensitive relaxation mechanism.

作为螯合配体的4-乙酰噻唑肟和作为刘易斯酸交联剂的苯硼酸在镍（II）离子上用其高氯酸盐模板缩合，得到了苯硼单包镍（II）中心三噻唑肟离子与ClO4−反阴离子的离子缔合。以金属（II）氯化物（M2+ = Fe2+, Co2+, Ni2+， Mn2+和Zn2+）为M2+离子源，形成相应的氯- h键伪大环配合物。从单晶x射线衍射数据可以看出，它们的伪大环结构是由CH…Cl -与噻唑肟酸合子的三个N， s杂环基团接触而形成的。Fe（II）、Co（II）和Zn（II）离子位于mn6 -三棱柱配位多面体的中心，而nin6 -多面体的几何形状介于三棱柱和三反棱柱之间。采用元素分析、PXRD、MALDI-TOF MS、UV-vis和NMR等方法对所制备的金属（II）假螯合物进行了表征。根据磁强计和x射线衍射数据，它们的金属（II）离子处于高自旋态。在SA-CASSCF/NEVPT2量子化学计算的支持下，交流和直流磁性研究表明，给定的钴（II）假螯合物由于未淬灭的角轨道动量而表现出很强的单轴磁性各向异性。它还证明了零场单分子磁体行为，磁化的量子隧穿是唯一的磁敏感弛豫机制。

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引用次数: 0

From coordination to protection: 1,10-phenanthroline-based Cu(II) complexes against metal corrosion 从配位到保护：1,10-菲罗啉基Cu（II）配合物抗金属腐蚀

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-04 DOI: 10.1016/j.poly.2025.117869

Hassan H. Hammud , Basem F. Ali , Waleed A. Aljamhi , Saurav Bhattacharya , Ulrich Kortz

A new one-dimensional thiocyanato bridged Cu(II) polynuclear coordination polymer containing 1,10-phenanthroline (phen), [Cu(phen)(μ-SCN)(μ-NCS)]_n (1), has been synthesized. Complex (1) has been characterized by elemental analyses and spectroscopic techniques. The X-ray single crystal structure of (1) shows the formation of polymeric chains of thiocyanate bridges. In the polymer, the Cu^II ion in an octahedral environment, coordinated by one phen and four thiocyanato ligands. Two of the thiocyanato ligands are N-bonded and the other two S-bonded forming a CuN₄S₂ core. Whereas the N atoms have almost linear Cu—N—C angles (164.4°), the S atoms are bonded with a Cu—S—C angle of 96.80°. All thiocyanato ligands are bridging Cu ions into one-dimensional chains. The lattice of (1), shows polymers connected through CH⋯S, offset-face-to-face π–π stacking interactions and S⋯S interactions consolidating a 3D structure. The supramolecular structures of bridged dimeric complexes bis[(μ²-chloro)chloro(phen)copper(II)] (2) and bis[(μ²-azido)-chloro-(phen)‑copper(II)] (3) were also briefly discussed. Comparative studies with the dimeric analogues (2) and (3) reveal that polymer (1) exhibits enhanced thermal stability, delaying phenanthroline release to higher temperature. Electrochemical impedance and potentiodynamic polarization measurements show all three complexes function as mixed-type corrosion inhibitors with predominant cathodic behaviour for C-steel in 0.25 M H₂SO₄. At optimal dosages, (1) achieves 73.3 % inhibition at 100 ppm, while (2) and (3) reach 95.1 % and 91.2 % at 120 ppm, respectively. Weight loss experiments confirmed the decrease in corrosion rates when the complexes were added to the blank 1 M HCl. The free energies calculated from Langmuir adsorption isotherms and SEM analysis confirm the formation of protective precipitates on the steel surface. These results highlight the critical influence of molecular topology on anticorrosion performance and identify the dimeric structures as particularly promising for steel protection.

合成了一种新的含1,10-菲罗啉（phen）的一维硫氰酸酯桥接Cu（II）多核配位聚合物[Cu(phen)(μ-SCN)(μ-NCS)]n(1)。配合物(1)已通过元素分析和光谱技术进行了表征。(1)的x射线单晶结构显示了硫氰酸酯桥聚合物链的形成。在聚合物中，CuII离子在一个八面体环境中，由一个phenen和四个硫氰酸酯配体配位。两个硫氰酸酯配体是n键的，另外两个是s键的，形成了一个CuN4S2核。而N原子的Cu-N-C角几乎为线性（164.4°），S原子的Cu-S-C角为96.80°。所有的硫氰酸酯配体都将铜离子桥接成一维链。(1)的晶格显示了通过CH⋯S，偏移面对面π -π堆叠相互作用和S⋯S相互作用连接的聚合物，巩固了3D结构。简要讨论了桥接二聚物双[（μ2-氯）氯（苯）铜（II）](2)和双[（μ2-叠氮）-氯-（苯）铜（II）](3)的超分子结构。与二聚物类似物(2)和(3)的比较研究表明，聚合物(1)表现出更强的热稳定性，延缓了菲罗啉向更高温度的释放。电化学阻抗和动电位极化测量表明，在0.25 M H2SO4中，这三种配合物都是混合型缓蚀剂，对c -钢具有主要的阴极行为。在最佳剂量下，(1)在100 ppm时的抑制率为73.3%，而(2)和(3)在120 ppm时的抑制率分别为95.1%和91.2%。失重实验证实，在空白的1 M HCl中加入配合物后，腐蚀速率降低。由Langmuir吸附等温线计算的自由能和SEM分析证实了钢表面有保护性沉淀的形成。这些结果突出了分子拓扑对防腐性能的关键影响，并确定了二聚体结构在钢的保护方面特别有前途。

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引用次数: 0

Synthesis of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate and its complexation properties towards hexavalent actinides: crystal structure and solvent extraction studies 膦酸二乙酯（5-乙基-2-羟基-3-硝基苯基）的合成及其对六价锕系元素的络合性能：晶体结构和溶剂萃取研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-04 DOI: 10.1016/j.poly.2025.117868

Alina Sivolap , Vladimir Baulin , Yuliana Rogacheva , Dmitriy Baulin , Alexander Fedoseev , Mikhail Grigoriev , Vladislav Sharov , Galina Kostikova

Complexes of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate with uranyl and neptunyl nitrates [UO₂(HL¹)₂(NO₃)₂] and [NpO₂(HL¹)₂(NO₃)₂] were synthesized and characterized for the first time. A procedure was developed for the preparation of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate by nitration of diethyl (5-ethyl-2-hydroxyphenyl)phosphonate with a solution of uranyl nitrate in acetonitrile, in the form of the complex [UO₂(HL¹)₂(NO₃)₂]. Using HCl, uranyl could be separated from the complex and, thus, the uncoordinated ligand HL¹ could be isolated and identified, which was subsequently used to prepare the complex [NpO₂(HL¹)₂(NO₃)₂] and in solvent extraction experiments. The extraction of U(VI) and Pu(VI) by HL¹ in 1,2-dichloroethane and meta-trifluoromethylnitrobenzene from nitric acid solutions was investigated.

首次合成了（5-乙基-2-羟基-3-硝基苯基）膦酸二乙酯与硝酸铀酰和硝酰[UO2(HL1)2(NO3)2]和[NpO2(HL1)2(NO3)2]配合物并对其进行了表征。研究了以硝酸铀酰溶液与磷酸二乙酯（5-乙基-2-羟基-3-硝基苯基）膦酸二乙酯（5-乙基-2-羟基-3-硝基）膦酸二乙酯(UO2（HL1)2(NO3)2）为配合物，在乙腈中硝化制备膦酸二乙酯的工艺。用HCl将铀酰从配合物中分离出来，从而分离和鉴定了不配位配体HL1，并将其用于制备配合物[NpO2(HL1)2(NO3)2]和溶剂萃取实验。研究了在硝酸溶液中1,2-二氯乙烷和间三氟甲基硝基苯中HL1萃取U（VI）和Pu（VI）的工艺。

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引用次数: 0