Polyhedron最新文献_第7页

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

Tandem synthesis of zinc tetrazolate complexes via [3 + 2] cyclo-addition at ambient condition and exploration of noncovalent interactions in their solid state structures 环境条件下[3 + 2]环加成串联合成四氮酸锌配合物及其固态结构中非共价相互作用的探索

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-03 DOI: 10.1016/j.poly.2025.117863

Md Gishan , Mridul Karmakar , Rosa M. Gomila , Antonio Frontera , Shouvik Chattopadhyay

We report the synthesis and structural characterization of three zinc(II) tetrazolate complexes [Zn(PTZ)₂(H₂O)₂] (1), [Zn(HL¹)(PTZ)]₂ (2), and [Zn(HL²)(PTZ)]₂ (3) obtained via in situ [3 + 2] cycloaddition of azide with 2-cyanopyridine under mild conditions [HPTZ = 5(2-pyridyl)tetrazole, H₂L¹ = 4-chloro-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol, H₂L² = 4-bromo-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol]. X-ray diffraction analysis reveals that complex 1 forms discrete mononuclear units that self-assemble into 2D hydrogen-bonded sheets, driven by directional OH⋯N interactions between the coordinated water molecules and the tetrazolate moieties, reinforced by π–π stacking. In contrast, the dinuclear complexes 2 and 3 exhibit bridging μ-NN-tetrazolate ligands and distorted octahedral coordination geometries. Surprisingly, their solid-state structures are stabilized by unconventional halogen⋯π interactions between the negatively charged Cl (in 2) or Br (in 3) atoms and the electron-rich π-system of Zn-bound phenolate rings. These counterintuitive contacts are supported by Hirshfeld surface analysis and will be rationalized through molecular electrostatic potential (MEP) surface analysis, energetically evaluated via DFT calculations, and further characterized using the Non-Covalent Interaction (NCIplot) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. This combined experimental and theoretical investigation provides new insights into the nature and strength of hydrogen bonding and halogen⋯π interactions in tetrazolate-based supramolecular assemblies.

本文报道了三种锌（II）四氮酸盐配合物[Zn(PTZ)2(H2O)2](1)、[Zn(HL1)(PTZ)]2(2)和[Zn(HL2)(PTZ)]2(3)在温和条件下通过叠氮化物与2-氰吡啶原位[3 + 2]环加成得到的[Zn（HL2)（PTZ)]2 （3) [HPTZ = 5（2-吡啶基）四氮唑，H2L1 = 4-氯-2-（（2-（2-羟乙基）氨基）亚氨基）甲基）苯酚，H2L2 = 4-溴-2-（（2-（2-羟乙基）氨基）乙基）亚氨基）甲基）苯酚]的合成和结构表征。x射线衍射分析表明，配合物1形成离散的单核单元，自组装成二维氢键片，由协调的水分子和四氮化基团之间的定向OH⋯N相互作用驱动，通过π -π堆叠加强。相反，双核配合物2和3表现出桥接μ- nn -四氮化盐配体和扭曲的八面体配位几何。令人惊讶的是，它们的固态结构是由带负电荷的Cl （in 2）或Br （in 3）原子与锌结合的酚酸环的富电子π系统之间的非常规卤素⋯π相互作用稳定的。这些反直觉的接触得到了Hirshfeld表面分析的支持，并将通过分子静电势（MEP）表面分析进行合理化，通过DFT计算进行能量评估，并使用非共价相互作用（NCIplot）和分子原子量子理论（QTAIM）方法进一步表征。这项结合实验和理论的研究为四氮酸盐基超分子组装中氢键和卤素π相互作用的性质和强度提供了新的见解。

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引用次数: 0

Tuning the magnetic anisotropy energy of MoS2-supported Mn12 complexes by electric field: A first-principles study 电场调节mos2负载的Mn12配合物的磁各向异性能：第一性原理研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-01 DOI: 10.1016/j.poly.2025.117865

Shuanglong Liu , Adam V. Bruce , Dmitry Skachkov , James N. Fry , Hai-Ping Cheng

In this work, we examine low-energy adsorption configurations of four dodecanuclear manganese single-molecule magnets

(Mn₁₂), where the ligand R being H, CH₃, CHCl₂ or C₆H₅, on a molybdenum disulfide (MoS₂) monolayer using force field and density functional theory calculations. The van der Waals interaction is shown to be crucial for determining the adsorption energy. Some electrons transfer from the substrate to the molecules upon surface adsorption, resulting in a reduction of the magnetic anisotropy energy of Mn₁₂. Since the lowest unoccupied molecular orbital of Mn₁₂ is close to the valence band of MoS₂, a negative electric field is more effective in modulating charge transfer and energy band alignment, and thus altering the magnetic anisotropy energy, compared with a positive electric field. A significant increase in the magnetic anisotropy energy of Mn₁₂ with the ligand

or

under a sufficiently high electric field has been predicted. Our calculations show that the molecules remain intact on the surface both before and after the electric field is applied. Finally, a two-level system formed by different adsorption configurations is evaluated, and the tunability of its energy barrier under an electric field is demonstrated. Our study sheds light on tuning the properties of single-molecule magnets using an electric field, when the molecules are supported on a surface.

在这项工作中，我们研究了四个十二核锰单分子磁体（Mn12）的低能吸附构型，其中配体R为H， CH3， CHCl2或C6H5，在二硫化钼（MoS2）单层上使用力场和密度功能理论计算。范德华相互作用被证明是决定吸附能的关键。一些电子通过表面吸附从衬底转移到分子中，导致Mn12的磁各向异性能降低。由于Mn12的最低未占据分子轨道靠近MoS2的价带，因此与正电场相比，负电场能更有效地调制电荷转移和能带排列，从而改变磁各向异性能。预测在配体作用下或在足够高的电场作用下，Mn12的磁各向异性能显著增加。我们的计算表明，在施加电场之前和之后，分子在表面上保持完整。最后，对不同吸附构型形成的两能级体系进行了评价，并证明了其能垒在电场作用下的可调性。我们的研究揭示了当分子被支撑在表面上时，使用电场来调整单分子磁体的特性。

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引用次数: 0

Harnessing photocatalytic activity of graphene covalently coupled TBA catalyst for oxygenation of sulfides using solar spectrum: Mechanistic studies and synthetic uses 利用太阳光谱利用石墨烯共价偶联TBA催化剂对硫化物氧化的光催化活性：机理研究和合成应用

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-10-31 DOI: 10.1016/j.poly.2025.117856

Naveen K. Yadav , Rajesh K. Yadav , Shaifali Mishra , Rehana Shahin , Kanchan Sharma , Vinay K. Mishra , Surendra K. Jaiswal , Ghadah Shukri Albakri , Maha Awjan Alreshidi , Krishna Kumar Yadav , Jin Ook Baeg

Solar-powered photocatalytic pathway introduces molecular oxygen into the sulfides. The pharmaceutical ingredient (sulfoxidation product) was transformed by harnessing sunlight to generate the necessary energy for the catalytic-oxidative reactions. The mechanistic pathway involves oxidants, which are green and sustainable reagents, i.e., oxygen/air, thereby maintaining aerobic oxidative and mild conditions. Herein, we develop an eco-friendly, reusable Gr@TBA photocatalyst via one-pot condensation of glucose-derived graphene (Gr) and 2,4,6-tribromoaniline (TBA). The Gr@TBA photocatalyst shows its excellent opto-electronic properties and charge separation capabilities by creating electron channels and also targets the chemo-selective (95 % sulfoxide selectivity at 90 % conversion) transformation to sulfoxide from sulfide.

太阳能光催化途径将分子氧引入硫化物中。药物成分（亚砜化产物）通过利用阳光产生催化氧化反应所需的能量而转化。机制途径涉及氧化剂，这是绿色和可持续的试剂，即氧气/空气，从而维持有氧氧化和温和的条件。在此，我们通过葡萄糖衍生的石墨烯（Gr）和2,4,6-三溴苯胺（TBA）的一锅缩合，开发了一种环保，可重复使用的Gr@TBA光催化剂。Gr@TBA光催化剂通过创建电子通道显示了其优异的光电性能和电荷分离能力，并且还针对硫化物转化为亚砜的化学选择性（90%转化率下95%亚砜选择性）。

引用次数: 0

Synthesis, solid state molecular structure, and cyclic voltammetry of a ruthenium nitrosyl porphyrin with a nitrosonaphthol ligand 含亚硝基萘酚配体的亚硝基卟啉钌的合成、固体分子结构和循环伏安法

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-10-30 DOI: 10.1016/j.poly.2025.117867

Nan Xu , Emily Suchta , Michael J. Shaw , Gadden Lych , Navamoney Arulsamy , Sela Cameron , Joshua Bueno

Nitrosonaphthols belong to the class of C-nitroso compounds, having an additional hydroxyl group on the naphthalene ring. Their coordination chemistry is rich due to the presence of both nitroso and hydroxyl groups. Despite the various binding modes of nitrosonaphthols in metal complexes, their interactions with heme model complexes remain unexplored. In this work, we report the synthesis and characterization of a six-coordinate ruthenium nitrosyl porphyrin complex, (OEP)Ru(NO)(η¹-ONC₁₀H₆O) from the reaction of excess 2-nitroso-1-naphthol with the nitrosyl ruthenium alkoxide precursor, (OEP)Ru(NO)(O-i-C₅H₁₁) (OEP = 2,3,7,8,12,13,17,18-octaethylporphinato dianion). The complex was characterized by various methods, including 1D and 2D NMR spectroscopy (COSY, HSQC, HMBC, and 1D-NOE), IR spectroscopy, and single-crystal X-ray crystallography. The molecular structure of (OEP)Ru(NO)(η¹-ONC₁₀H₆O) reveals monodentate O-binding to the metal through the nitroso oxygen atom of the oxo-oxime tautomer. The intermolecular interactions within the crystalline packing of the complex were investigated using Hirshfeld surface analysis. In addition, the redox behavior of (OEP)Ru(NO)(η¹-ONC₁₀H₆O) was studied through cyclic voltammetry in CH₂Cl₂. As far as we know, the structure of (OEP)Ru(NO)(η¹-ONC₁₀H₆O) represents the first member of the class of monodentate 1,2-nitrosonaphthol metal complexes.

亚硝基萘酚属于c -亚硝基化合物，在萘环上有一个额外的羟基。由于亚硝基和羟基的存在，它们的配位化学丰富。尽管亚硝基萘酚在金属配合物中的结合模式多种多样，但它们与血红素模型配合物的相互作用仍未被探索。本文报道了过量的2-亚硝基-1-萘酚与亚硝基醇化钌前驱体（OEP）Ru(NO)(O-i-C5H11) （OEP = 2,3,7,8,12,13,17,18-八烷基卟啉）反应合成六配位钌亚硝基卟啉配合物（OEP）Ru(NO)（η -1- onc10h60）并对其进行了表征。通过1D和2D NMR波谱（COSY、HSQC、HMBC和1D- noe）、IR光谱和单晶x射线晶体学等方法对该配合物进行了表征。（OEP）Ru(NO)（η - 1- onc10h60）的分子结构显示单齿o通过氧肟互变体的亚硝基氧原子与金属结合。利用Hirshfeld表面分析方法研究了该配合物晶体填料内的分子间相互作用。此外，通过循环伏安法研究了（OEP）Ru(NO)（η - 1- onc10h60）在CH2Cl2中的氧化还原行为。据我们所知，（OEP）Ru(NO)（η - 1- onc10h60）的结构是单齿1,2-亚硝基萘酚类金属配合物的第一分子。

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