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Emerging Pd-based electrocatalysts and supports for ethanol oxidation reaction: High-entropy and single-atom materials 用于乙醇氧化反应的新兴钯基电催化剂和支持物:高熵和单原子材料
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-18 DOI: 10.1016/j.ica.2024.122377
Alkaline direct ethanol fuel cells (ADEFCs) offer a promising solution to reduce reliance on fossil fuels. Despite their advantages over hydrogen and methanol fuel cells, the anodic ethanol oxidation reaction (EOR) in ADEFCs faces challenges such as sluggish kinetics and high overpotentials, leading to reduced efficiency. To address these issues, highly active electrocatalysts are essential. This review highlights recent advancements in Pd-based high-entropy materials (HEMs) and single-atom catalysts (SACs) for EOR. Additionally, MXenes, a novel family of two-dimensional materials, have shown promise as supports for these electrocatalysts. We discuss the fundamental principles of EOR, the unique properties of these emerging materials, and their applications in EOR electrocatalysis. Finally, we provide an outlook on future research directions to enhance the commercialization of Pd-based electrocatalysts for ADEFC technologies.
碱性直接乙醇燃料电池(ADEFCs)为减少对化石燃料的依赖提供了一种前景广阔的解决方案。尽管与氢燃料电池和甲醇燃料电池相比,ADEFCs 中的阳极乙醇氧化反应(EOR)具有优势,但也面临着一些挑战,如动力学缓慢和过电位高,从而导致效率降低。要解决这些问题,高活性电催化剂必不可少。本综述重点介绍了用于 EOR 的钯基高熵材料 (HEM) 和单原子催化剂 (SAC) 的最新进展。此外,新型二维材料系列 MXenes 已显示出作为这些电催化剂载体的前景。我们将讨论 EOR 的基本原理、这些新兴材料的独特性质及其在 EOR 电催化中的应用。最后,我们对未来的研究方向进行了展望,以促进用于 ADEFC 技术的钯基电催化剂的商业化。
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引用次数: 0
Tridentate chelating ligand coordinated Co(III) complexes: Synthesis, crystal structure, DFT/TD-DFT calculation, studies of interaction with proteins and molecular docking 三叉螯合配体配位的 Co(III) 复合物:合成、晶体结构、DFT/TD-DFT 计算、与蛋白质的相互作用以及分子对接研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-18 DOI: 10.1016/j.ica.2024.122379
This research article encompasses the synthesis of two novel mononuclear cobalt(III) complexes of ONO donor tridentate Schiff base ligands, [Co(HL)2]∙(HCDA) (1) and [Co(L1)2]∙(5H2O)∙(Et3NH) (2) [H2L = (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)), HCDA = 1,4-cyclohexanemonocarboxylate, H2L1 = 3-[(2-hydroxy-3-methoxy-benzylidine)-amino]-propionic acid, Et3NH = protonated triethylamine] and characterization of these compounds through the spectroscopic studies and X-ray diffraction techniques. Structural determination reveals that both the complexes crystallize in the triclinic system with space group P-1 and exhibits six coordinated distorted octahedral geometry. DFT as well as TD-DFT calculations were performed using WB97XD/DGTZVP method to understand the electronic properties and stability of the complexes. The computational results are in accordance with the experimental results. Based on the results of quantum chemical parameters, it is found that complex 1 is more reactive, more electrophile less hard and has higher electronegativity value than that of complex 2. The binding efficacy and binding mode of these complexes with bovine serum albumin and human serum albumin are investigated through experimental and computational approaches, including molecular docking studies to assess their potential biological applications. The hyperchromism in electronic absorption spectra and quenching of fluorescence intensities of serum albumins with various complex concentrations illustrate the presence of strong interaction between the serum albumins and the studied complexes. Kinetic parameters of interactions reveal that the binding affinities of the tested complexes are comparable with the reported Schiff base coordinated cobalt complexes. Molecular docking results show that both the complexes, selectively binds with the bovine serum albumin at the active site Tyr 149 and with human serum albumin at the active site Tyr 411 via hydrophobic, electrostatic and hydrogen bonding interactions. The binding affinity of the complexes with serum albumins follow the order 2 > 1 which may be due to the higher HOMO energy of 2 is capable to donate electrons easily to the receptors.
本研究文章包括两种新型单核钴(III)配合物的合成:[Co(HL)2]∙(HCDA) (1)和[Co(L1)2]∙(5H2O)∙(Et3NH) (2) [H2L = (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)) 、HCDA = 1,4-环己基柠檬羧酸盐,H2L1 = 3-[(2-羟基-3-甲氧基-苄基)氨基]-丙酸,Et3NH = 质子化三乙胺],并通过光谱研究和 X 射线衍射技术对这些化合物进行表征。结构测定结果表明,这两种复合物都在空间群为 P-1 的三菱系中结晶,并呈现出六配位畸变八面体几何形状。为了了解复合物的电子特性和稳定性,我们使用 WB97XD/DGTZVP 方法进行了 DFT 和 TD-DFT 计算。计算结果与实验结果一致。根据量子化学参数的计算结果发现,络合物 1 比络合物 2 反应性更强、亲电性更弱、电负性更高。通过实验和计算方法,包括分子对接研究,研究了这些复合物与牛血清白蛋白和人血清白蛋白的结合效能和结合模式,以评估其潜在的生物学应用。电子吸收光谱中的高色度以及不同复合物浓度下血清白蛋白荧光强度的淬灭表明,血清白蛋白与所研究的复合物之间存在强烈的相互作用。相互作用的动力学参数表明,测试的配合物的结合亲和力与已报道的希夫碱配位钴配合物相当。分子对接结果表明,这两种复合物都能通过疏水、静电和氢键相互作用,选择性地与活性位点 Tyr 149 上的牛血清白蛋白和活性位点 Tyr 411 上的人血清白蛋白结合。复合物与血清白蛋白的结合亲和力按照 2 > 1 的顺序排列,这可能是由于 2 的 HOMO 能量较高,能够很容易地向受体提供电子。
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引用次数: 0
The effect of metal centers on the electronic transitions of HOMO- and heteronuclear Ru(Ⅱ) and Os(Ⅱ) complexes with 2,3,5,6-tetrakis(2-pyridyl) pyrazine: A combined theoretical and experimental study 金属中心对 2,3,5,6-四(2-吡啶基)吡嗪 HOMO 和杂核 Ru(Ⅱ) 和 Os(Ⅱ) 配合物电子跃迁的影响:理论与实验的综合研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-16 DOI: 10.1016/j.ica.2024.122383

This study investigates the impact of the type and arrangement of metal centers on the electronic transitions of multimetallic complexes through a combined experimental and computational approach. At first, homo- and hetero-metallic [Mn(TPPZ)n+1]2n+ complexes (M = Ru(Ⅱ) and Os(Ⅱ), TPPZ = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and n = 1 and 2) were synthesized and fully characterized. Then, density functional theory (DFT) and time-dependent DFT calculations were performed to explore the geometries, electronic structures, excited states, and spectroscopic properties of mono-, bi-, and trimetallic complexes. The comparison between experimental and computational spectra of mono- and bimetallic complexes showed excellent agreement, particularly in peak intensities and absorption energies. The visible region bands were attributed to metal-to-ligand charge-transfer (MLCT) transitions. This study offers insights into how the quantity, type, and arrangement of metal centers influence the frontier orbital energy levels and electronic spectra in homo- and heteronuclear complexes.

本研究通过实验和计算相结合的方法,研究了金属中心的类型和排列对多金属配合物电子跃迁的影响。首先,合成并充分表征了同金属和杂金属 [Mn(TPPZ)n+1]2n+ 复合物(M = Ru(Ⅱ) 和 Os(Ⅱ),TPPZ = 2,3,5,6-四(2-吡啶基)吡嗪,n = 1 和 2)。然后,通过密度泛函理论(DFT)和随时间变化的 DFT 计算,探索了单金属、双金属和三金属配合物的几何结构、电子结构、激发态和光谱特性。单金属和双金属配合物的实验光谱与计算光谱之间的比较显示出极好的一致性,尤其是在峰强度和吸收能量方面。可见光区带归因于金属-配体电荷转移(MLCT)跃迁。这项研究有助于深入了解金属中心的数量、类型和排列如何影响同核和异核配合物的前沿轨道能级和电子光谱。
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引用次数: 0
Ruthenium(II) complexes bearing tridentate 2-(methylsulfoxide)-phenylsalicylaldimine Schiff-base ligands 带有三叉 2-(甲基亚砜)-苯基水杨醛亚胺席夫碱配体的钌(II)配合物
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-14 DOI: 10.1016/j.ica.2024.122373

The sulfoxide-containing Schiff base (E)-2-((2-(methylsulfinylphenyl)imino) methyl) phenol (HL) was synthesized by aldolamine condensation and oxidation. In the presence of triethylamine, equal amounts of [RuCl2(CO)2]n, [RuHCl(CO)(PPh3)3], cis-[RuCl2(dmso)4] (dmso = dimethylsulfoxide) and [RuCl2(PPh3)3] were reacted with HL to give the ruthenium(II) complexes [RuCl(L)(CO)2] (1), [RuCl(L)(CO)(PPh3)] (2), [RuCl(L)(dmso)2] (3), and [RuCl(L)(PPh3)2] (4), respectively. Compound 4 converted to be [RuCl(L)(PPh3)(CH3CN)] (4′) by recrystallization in acetonitrile. The structures of HL, 1, 2, 3 and 4′ have been confirmed by single crystal X-ray crystallography. In addition, the UV–visible, infrared and fluorescence spectra of HL and its ruthenium complexes 14 along with their electrochemical properties were investigated. The catalytic properties of complexes 14 for the cyclopropylation of styrene were also presented.

通过醛胺缩合和氧化合成了含氧化硫的希夫碱 (E)-2-((2-(甲亚磺酰基苯基)亚氨基)甲基) 苯酚 (HL)。在三乙胺存在下,等量的[RuCl2(CO)2]n、[RuHCl(CO)(PPh3)3]、顺式[RuCl2(dmso)4](dmso=二甲基亚砜)和[RuCl2(PPh3)3]与 HL 反应,得到钌(II)配合物[RuCl(L)(CO)2](1)、[RuCl(L)(CO)(PPh3)] (2)、[RuCl(L)(dmso)2] (3) 和 [RuCl(L)(PPh3)2] (4)。化合物 4 在乙腈中重结晶为[RuCl(L)(PPh3)(CH3CN)](4′)。HL、1、2、3 和 4′的结构已由单晶 X 射线晶体学证实。此外,还研究了 HL 及其钌配合物 1-4 的紫外可见光谱、红外光谱和荧光光谱,以及它们的电化学性质。此外,还介绍了配合物 1-4 在苯乙烯环丙基化过程中的催化特性。
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引用次数: 0
Structure-dependent aggregation and ROS-generation in aqueous media of new cationic copper(I) complexes based on 1,5,3,7-diazadiphosphacyclooctanes 基于 1,5,3,7-二氮二磷杂环辛烷的新型阳离子铜(I)配合物在水介质中的结构依赖性聚集和 ROS 生成
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-14 DOI: 10.1016/j.ica.2024.122382

This work presents the synthesis of new cationic bis-(P,P)-chelate copper(I) tetrafluoroborate and hexafluorophosphate complexes with 1,5,3,7-diazadiphosphacyclooctanes with various para-alkylphenyl substituents (alkyl – methyl, isopropyl and octyl) at nitrogen atoms to assess their effect on the therapeutic potential of these complexes. Structure-dependent aggregation of these complexes is observed in the aqueous medium simulating nutrient media, with the octyl-substituted complex exhibiting the most pronounced aggregation. The generation of reactive oxygen species (ROS) by the complexes in an aqueous environment does not correlate with their oxidation potentials but is significantly suppressed by their aggregation. The luminescence of the complexes in the aqueous environment enables the visualization of their cellular uptake. This allows to correlate the cellular uptake of the complexes with their structure-dependent aggregation. The cytotoxicity of the complexes measured in a range of cancer and normal cells depends on their structure, which can be explained by their structure-dependent aggregation and ROS generation. The anticancer specificity of the complexes with isopropylphenyl and methylphenyl substituents are comparable, while these values are higher compared to the octyl-substituted complex. Therefore, these groups are optimal for ensuring the anticancer specificity of Cu(I) bis-chelates, which is likely due to the formation of aggregates with sufficient chemical and colloidal stability in aqueous media.

本研究提出了一种新的阳离子双(P,P)-螯合四氟硼酸铜(I)和六氟磷酸铜(I)与氮原子上具有各种对位烷基苯基取代基(烷基-甲基、异丙基和辛基)的 1,5,3,7- 二氮杂二磷杂环辛烷配合物的合成方法,以评估它们对这些配合物治疗潜力的影响。在模拟营养介质的水介质中观察到了这些复合物的结构依赖性聚集现象,其中辛基取代的复合物的聚集现象最为明显。络合物在水环境中产生的活性氧(ROS)与其氧化电位无关,但其聚集作用会显著抑制活性氧的产生。复合物在水环境中发出的荧光可使其细胞摄取量可视化。这样就可以将细胞对复合物的吸收与复合物结构相关的聚集联系起来。在一系列癌细胞和正常细胞中测得的复合物细胞毒性取决于它们的结构,这可以通过它们的结构依赖性聚集和 ROS 生成来解释。具有异丙基苯基和甲基苯基取代基的复合物的抗癌特异性相当,而辛基取代基复合物的抗癌特异性更高。因此,这些基团是确保 Cu(I)双螯合物抗癌特异性的最佳基团,这可能是由于在水介质中形成了具有足够化学稳定性和胶体稳定性的聚集体。
{"title":"Structure-dependent aggregation and ROS-generation in aqueous media of new cationic copper(I) complexes based on 1,5,3,7-diazadiphosphacyclooctanes","authors":"","doi":"10.1016/j.ica.2024.122382","DOIUrl":"10.1016/j.ica.2024.122382","url":null,"abstract":"<div><p>This work presents the synthesis of new cationic bis-(P,P)-chelate copper(I) tetrafluoroborate and hexafluorophosphate complexes with 1,5,3,7-diazadiphosphacyclooctanes with various <em>para</em>-alkylphenyl substituents (alkyl – methyl, isopropyl and octyl) at nitrogen atoms to assess their effect on the therapeutic potential of these complexes. Structure-dependent aggregation of these complexes is observed in the aqueous medium simulating nutrient media, with the octyl-substituted complex exhibiting the most pronounced aggregation. The generation of reactive oxygen species (ROS) by the complexes in an aqueous environment does not correlate with their oxidation potentials but is significantly suppressed by their aggregation. The luminescence of the complexes in the aqueous environment enables the visualization of their cellular uptake. This allows to correlate the cellular uptake of the complexes with their structure-dependent aggregation. The cytotoxicity of the complexes measured in a range of cancer and normal cells depends on their structure, which can be explained by their structure-dependent aggregation and ROS generation. The anticancer specificity of the complexes with isopropylphenyl and methylphenyl substituents are comparable, while these values are higher compared to the octyl-substituted complex. Therefore, these groups are optimal for ensuring the anticancer specificity of Cu(I) bis-chelates, which is likely due to the formation of aggregates with sufficient chemical and colloidal stability in aqueous media.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004730/pdfft?md5=fe6712f6776959a047dcfb7f841f8778&pid=1-s2.0-S0020169324004730-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142232523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Structure search for transition metal clusters. Towards a rational understanding of their size-dependent properties 过渡金属簇的结构搜索。实现对其尺寸相关特性的理性认识
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-14 DOI: 10.1016/j.ica.2024.122376
Prediction of the lowest energy structure for transition metal clusters and related systems is fundamental in cluster science. Advances in the structure search methods have reduced the computer time for structure prediction, standing on the performance of density functional theory (DFT) calculations. This perspective summarizes recent advances in the employed strategies to tackle geometrical determination of small and large metallic clusters via structure identification and rationalization of the resulting properties. Particularly, we pay attention to coinage metal clusters and noble metals due to their potential technological applications. The basics and recent achievements in structure search methods and related challenges are summarized, towards determining structural evolution accounting contributing to further development on efficient catalytic materials among other applications of technological interest.
预测过渡金属簇和相关系统的最低能量结构是簇科学的基础。基于密度泛函理论(DFT)计算的性能,结构搜索方法的进步缩短了结构预测的计算机时间。本视角总结了通过结构识别和合理化所产生的性质来解决大小金属团簇几何确定问题的策略的最新进展。我们尤其关注硬币金属簇和贵金属,因为它们具有潜在的技术应用价值。本文总结了结构搜索方法的基本原理和最新成果以及相关挑战,旨在确定结构演变,为进一步开发高效催化材料及其他技术应用做出贡献。
{"title":"Structure search for transition metal clusters. Towards a rational understanding of their size-dependent properties","authors":"","doi":"10.1016/j.ica.2024.122376","DOIUrl":"10.1016/j.ica.2024.122376","url":null,"abstract":"<div><div>Prediction of the lowest energy structure for transition metal clusters and related systems is fundamental in cluster science. Advances in the structure search methods have reduced the computer time for structure prediction, standing on the performance of density functional theory (DFT) calculations. This perspective summarizes recent advances in the employed strategies to tackle geometrical determination of small and large metallic clusters via structure identification and rationalization of the resulting properties. Particularly, we pay attention to coinage metal clusters and noble metals due to their potential technological applications. The basics and recent achievements in structure search methods and related challenges are summarized, towards determining structural evolution accounting contributing to further development on efficient catalytic materials among other applications of technological interest.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319072","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
Synthesis, crystal structures and properties of three sodium coordination polymers based on bridging polyoxometalate ligands 基于桥接聚氧化金属配体的三种钠配位聚合物的合成、晶体结构和性质
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-13 DOI: 10.1016/j.ica.2024.122380

The syntheses, crystal structures, spectral characterization, electrochemical, photoredox properties and biological studies of three sodium coordination polymers viz. (ImH)4[(µ2-HMo7O24)Na(H2O)8]∙7H2O 1 (Im = Imidazole), [(TEAH)Na5(H2O)12(µ5-Mo7O24)] 2 (TEA=triethanolamine) and [Na2(PyrH)2(µ2-Mo8O26)(H2O)7]∙8H2O 3 (Pyr = pyrazole) are reported. The unique Na atom in 1 exhibits ten coordination unlike hexa coordination observed in 2 and 3. The µ2-bridging heptamolybdate (or octamolybdate) anion in 1 (or 3) links the sodium cations into an infinite chain resulting in a one-dimensional coordination polymer. In 2, the heptamolybdate anion exhibits an unprecedented µ5-nonadentate binding resulting in a three- dimensional (3D) structure. Compounds 13 exhibit characteristic Raman bands. Solar irradiation of 2 results in photodimerization, which is further supported by electrochemical studies. Compounds 13 exhibit antibacterial activity, with 3 being the most effective against S. Pyogenes, followed by P. aeruginosa, S.typhi and S. aureus. Compound 3 exhibits excellent antidiabetic and anti-inflammatory properties. A comparative study of the binding modes of several heptamolybdates and octamolybdates based compounds is presented.

三种钠配位聚合物的合成、晶体结构、光谱表征、电化学、光氧化性能和生物学研究,即(ImH)4[(µ2-HMo7O24)Na(H2O)8]∙7H2O 1(Im=咪唑)、[(TEAH)Na5(H2O)12(µ5-Mo7O24)] 2(TEA=三乙醇胺)和[Na2(PyrH)2(µ2-Mo8O26)(H2O)7]∙8H2O 3(Pyr=吡唑)。与在 2 和 3 中观察到的六配位不同,1 中唯一的 Na 原子呈现十配位。在 1(或 3)中,μ2 桥接七钼酸盐(或八钼酸盐)阴离子将钠离子连接成无限链,形成一维配位聚合物。在 2 中,七钼酸盐阴离子表现出前所未有的 µ5-nonadentate 结合,形成三维(3D)结构。化合物 1-3 显示出特征性拉曼带。太阳光照射 2 会导致光二聚化,电化学研究进一步证实了这一点。化合物 1-3 具有抗菌活性,其中 3 对化脓性疽杆菌最有效,其次是铜绿假单胞菌、伤寒杆菌和金黄色葡萄球菌。化合物 3 具有出色的抗糖尿病和抗炎特性。本文对几种七钼酸盐和八钼酸盐化合物的结合模式进行了比较研究。
{"title":"Synthesis, crystal structures and properties of three sodium coordination polymers based on bridging polyoxometalate ligands","authors":"","doi":"10.1016/j.ica.2024.122380","DOIUrl":"10.1016/j.ica.2024.122380","url":null,"abstract":"<div><p>The syntheses, crystal structures, spectral characterization, electrochemical, photoredox properties and biological studies of three sodium coordination polymers viz. (ImH)<sub>4</sub>[(µ<sub>2</sub>-HMo<sub>7</sub>O<sub>24</sub>)Na(H<sub>2</sub>O)<sub>8</sub>]∙7H<sub>2</sub>O <strong>1</strong> (Im = Imidazole), [(TEAH)Na<sub>5</sub>(H<sub>2</sub>O)<sub>12</sub>(<em>µ<sub>5</sub></em>-Mo<sub>7</sub>O<sub>24</sub>)] <strong>2</strong> (TEA=triethanolamine) and [Na<sub>2</sub>(PyrH)<sub>2</sub>(<em>µ<sub>2</sub></em>-Mo<sub>8</sub>O<sub>26</sub>)(H<sub>2</sub>O)<sub>7</sub>]∙8H<sub>2</sub>O <strong>3</strong> (Pyr = pyrazole) are reported. The unique Na atom in <strong>1</strong> exhibits ten coordination unlike hexa coordination observed in <strong>2</strong> and <strong>3</strong>. The µ<sub>2</sub>-bridging heptamolybdate (or octamolybdate) anion in <strong>1</strong> (or <strong>3</strong>) links the sodium cations into an infinite chain resulting in a one-dimensional coordination polymer. In <strong>2,</strong> the heptamolybdate anion exhibits an unprecedented <em>µ<sub>5</sub></em>-nonadentate binding resulting in a three- dimensional (3D) structure. Compounds <strong>1</strong>–<strong>3</strong> exhibit characteristic Raman bands. Solar irradiation of <strong>2</strong> results in photodimerization, which is further supported by electrochemical studies. Compounds <strong>1</strong>–<strong>3</strong> exhibit antibacterial activity, with <strong>3</strong> being the most effective against <em>S. Pyogenes</em>, followed by <em>P. aeruginosa</em>, <em>S.typhi</em> and <em>S. aureus</em>. Compound <strong>3</strong> exhibits excellent antidiabetic and anti-inflammatory properties. A comparative study of the binding modes of several heptamolybdates and octamolybdates based compounds is presented.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004717/pdfft?md5=47e792addf54a098e197e056965c7fa7&pid=1-s2.0-S0020169324004717-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis and crystal structure of the complex [Rb3(CYH2)3(CYH3)(H2O)4] (CYH3 = isocyanuric acid): An interesting case of disordered sub-structure, ordered super-structure 复合物 [Rb3(CYH2)3(CYH3)(H2O)4](CYH3 = 异氰尿酸)的合成与晶体结构:无序亚结构、有序超结构的有趣案例
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-13 DOI: 10.1016/j.ica.2024.122378
The reaction in water between RbOH and isocyanuric acid (CYH3) leads, under mild reaction conditions (pH = 10, T = 20 °C), to the formation of crystals of good quality of the complex [Rb3(CYH2)3(CYH3)(H2O)4]. The ordered structure of [Rb3(CYH2)3(CYH3)(H2O)4] was refined from X-ray diffraction data, using a super-structure unit cell with a = 13.1315(1), b = 16.6198(1), c = 23.6865(1) Å, β = 99.751(1)°, and space group I2/a. The asymmetric unit of [Rb3(CYH2)3(CYH3)(H2O)4] contains three independent Rb+ cations, three CYH2 anions, one CYH3 and four water molecules, all located in the unit cell in general position. The Rb+ cations with the water molecules are arranged to form layers intercalated by ribbons made by the CYH2 anions and CYH3 molecules, in their keto-tautomeric form, that are coordinated to the cations through their oxygen atom, and interact each other and with the water molecules through hydrogen bonds. FT-IR and ATR-IR spectra of complex [Rb3(CYH2)3(CYH3)(H2O)4] are reported. Hirshfeld surface analysis (dnorm, shape index, curvedness) was also used to visualize the intermolecular interactions in the crystal structure. The low value of void percent in the crystal packing, to which the presence of water molecules contribute, indicates a compact crystal packing.
在温和的反应条件下(pH = 10,T = 20 °C),RbOH 和异氰尿酸(CYH3)在水中发生反应,形成了品质优良的复合物 [Rb3(CYH2)3(CYH3)(H2O)4]。根据 X 射线衍射数据完善了[Rb3(CYH2)3(CYH3)(H2O)4]的有序结构,其超结构单元晶胞为 a = 13.1315(1)、b = 16.6198(1)、c = 23.6865(1)埃、β = 99.751(1)°,空间群为 I2/a。[Rb3(CYH2)3(CYH3)(H2O)4]的不对称单元包含三个独立的 Rb+ 阳离子、三个 CYH2- 阴离子、一个 CYH3 和四个水分子,它们都位于单元格中的一般位置。Rb+ 阳离子与水分子排列成由 CYH2- 阴离子和 CYH3 分子组成的带状夹层,CYH2- 阴离子和 CYH3 分子为酮同分异构体形式,通过氧原子与阳离子配位,并通过氢键与水分子相互作用。报告了[Rb3(CYH2)3(CYH3)(H2O)4]复合物的 FT-IR 和 ATR-IR 光谱。此外,还采用了 Hirshfeld 表面分析法(dnorm、形状指数、弯曲度)来观察晶体结构中的分子间相互作用。由于水分子的存在,晶体堆积的空隙率值较低,这表明晶体堆积紧密。
{"title":"Synthesis and crystal structure of the complex [Rb3(CYH2)3(CYH3)(H2O)4] (CYH3 = isocyanuric acid): An interesting case of disordered sub-structure, ordered super-structure","authors":"","doi":"10.1016/j.ica.2024.122378","DOIUrl":"10.1016/j.ica.2024.122378","url":null,"abstract":"<div><div>The reaction in water between RbOH and isocyanuric acid (CYH<sub>3</sub>) leads, under mild reaction conditions (pH = 10, <em>T</em> = 20 °C), to the formation of crystals of good quality of the complex [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>]. The ordered structure of [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] was refined from X-ray diffraction data, using a super-structure unit cell with <em>a</em> = 13.1315(1), <em>b</em> = 16.6198(1), <em>c</em> = 23.6865(1) Å, β = 99.751(1)°, and space group <em>I</em>2<em>/a</em>. The asymmetric unit of [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] contains three independent Rb<sup>+</sup> cations, three CYH<sub>2</sub><sup>−</sup> anions, one CYH<sub>3</sub> and four water molecules, all located in the unit cell in general position. The Rb<sup>+</sup> cations with the water molecules are arranged to form layers intercalated by ribbons made by the CYH<sub>2</sub><sup>−</sup> anions and CYH<sub>3</sub> molecules, in their keto-tautomeric form, that are coordinated to the cations through their oxygen atom, and interact each other and with the water molecules through hydrogen bonds. FT-IR and ATR-IR spectra of complex [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] are reported. Hirshfeld surface analysis (<em>d</em><sub>norm</sub>, shape index, curvedness) was also used to visualize the intermolecular interactions in the crystal structure. The low value of void percent in the crystal packing, to which the presence of water molecules contribute, indicates a compact crystal packing.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004699/pdfft?md5=aa4857fdcb392ca39fc19841d28829af&pid=1-s2.0-S0020169324004699-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Density functional theory study of substituent effects on gas-phase heterolytic Fe-N bond energies of m-G-C6H4NHFe(CO)2(η5-C5H5) and m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5) 取代基对 m-G-C6H4NHFe(CO)2(η5-C5H5) 和 m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5) 的气相异解 Fe-N 键能影响的密度泛函理论研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-12 DOI: 10.1016/j.ica.2024.122370
The nature and strength of metal–ligand bonds in organotransition-metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe-N bond energies of meta-substituted anilinyldicarbonyl(η5-cyclopentadienyl)iron [m-G-C6H4NH(η5-C5H5)Fe(CO)2, abbreviated as m-G-C6H4NHFp (1), where G=NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO and NMe2] and meta-substituted α-acetylanilinyldicarbonyl(η5-cyclopentadienyl)iron [m-G-C6H4N(COMe)(η5-C5H5)Fe(CO)2, abbreviated as m-G-C6H4N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔHhet(Fe-N)′s. ΔΔHhet(Fe-N)′s (1 and 2) conform to the captodative principle. There are excellent linear free energy relations among ΔΔHhet(Fe-N)′s and the experimental and computational substituent effects on acidities of m-G-C6H4NH2, the differences of acidic dissociation constants (ΔpKas) of NH bonds for m-G-C6H4NH2 for series 1 or the substituent σm constants. The former correlations imply that the govering factors for these bond scissions are similar; the latter ones suggest that polar effects of meta-substituents show the dominant role to the magnitudes of ΔHhet(Fe-N)′s. And these correlations are in accordance with Hammett linear free energy relationships. The Fe-N bonds in series 1 are stronger than those in series 2. Therefore m-G-C6H4N(COMe)- are more stable than m-G-C6H4NH-. The absolute magnitudes of AEs, AEα-COMes and AEα-COMe, para-Gs are far larger than MEs, MEα-COMes and MEα-COMe, para-Gs. The influences of MEs, MEα-COMes and MEα-COMe, para-Gs are subtle. A better understanding of organometallic bond energies can suggest whether proposed new catalytic systems may work well.
有机过渡金属配合物中金属配体键的性质和强度对于理解有机金属反应和催化作用至关重要。不同理论水平的量子化学计算被用来研究元取代苯胺基二羰基(η5-环戊二烯基)铁[m-G-C6H4NH(η5-C5H5)Fe(CO)2,缩写为 m-G-C6H4NHFp (1)]的异溶解 Fe-N 键能、其中 G=NO2、CN、COMe、CO2Me、CF3、Br、Cl、F、H、Me、MeO 和 NMe2]以及元取代的 α-乙酰苯胺基二羰基(η5-环戊二烯基)铁[m-G-C6H4N(COMe)(η5-C5H5)Fe(CO)2,缩写为 m-G-C6H4N(COMe)Fp (2)]配合物。结果表明,在研究ΔHhet(Fe-N)′s 时,BP86 和 TPSSTPSS 具有最佳的性价比和更精确的预测。ΔΔHhet(Fe-N)′s与实验和计算中取代基对 m-G-C6H4NH2 酸性的影响、1 系列 m-G-C6H4NH2 NH 键酸性解离常数 (ΔpKas)的差异或取代基 σm 常数之间存在极好的线性自由能关系。前者的相关性意味着这些键裂解的影响因素是相似的;后者则表明元取代基的极性效应对 ΔHhet(Fe-N)′s的大小起着主导作用。这些相关性与 Hammett 线性自由能关系相一致。系列 1 中的 Fe-N 键比系列 2 中的强。因此,m-G-C6H4N(COMe)- 比 m-G-C6H4NH- 更稳定。AEs, AEα-COMes 和 AEα-COMe, para-Gs 的绝对值远远大于 MEs, MEα-COMes 和 MEα-COMe, para-Gs。MEs、MEα-COMes 和 MEα-COMe, para-Gs 的影响是微妙的。更好地了解有机金属键的能量可以说明所提出的新催化体系是否能很好地发挥作用。
{"title":"Density functional theory study of substituent effects on gas-phase heterolytic Fe-N bond energies of m-G-C6H4NHFe(CO)2(η5-C5H5) and m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5)","authors":"","doi":"10.1016/j.ica.2024.122370","DOIUrl":"10.1016/j.ica.2024.122370","url":null,"abstract":"<div><div>The nature and strength of metal–ligand bonds in organotransition-metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe-N bond energies of <em>meta</em>-substituted anilinyldicarbonyl(η<sup>5</sup>-cyclopentadienyl)iron [<em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub>, abbreviated as <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NHFp (<strong>1</strong>), where G=NO<sub>2</sub>, CN, COMe, CO<sub>2</sub>Me, CF<sub>3</sub>, Br, Cl, F, H, Me, MeO and NMe<sub>2</sub>] and <em>meta</em>-substituted α-acetylanilinyldicarbonyl(η<sup>5</sup>-cyclopentadienyl)iron [<em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub>, abbreviated as <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)Fp (<strong>2</strong>)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of Δ<em>H</em><sub>het</sub>(Fe-N)′s. ΔΔ<em>H</em><sub>het</sub>(Fe-N)′s (<strong>1</strong> and <strong>2</strong>) conform to the captodative principle. There are excellent linear free energy relations among ΔΔ<em>H</em><sub>het</sub>(Fe-N)′s and the experimental and computational substituent effects on acidities of <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub>, the differences of acidic dissociation constants (Δp<em>K</em><sub>a</sub>s) of N<img>H bonds for <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub> for series <strong>1</strong> or the substituent σ<sub>m</sub> constants. The former correlations imply that the govering factors for these bond scissions are similar; the latter ones suggest that polar effects of <em>meta</em>-substituents show the dominant role to the magnitudes of Δ<em>H</em><sub>het</sub>(Fe-N)′s. And these correlations are in accordance with Hammett linear free energy relationships. The Fe-N bonds in series <strong>1</strong> are stronger than those in series <strong>2</strong>. Therefore <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)<sup>-</sup> are more stable than <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sup>-</sup>. The absolute magnitudes of AEs, AE<sub>α-COMe</sub>s and AE<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s are far larger than MEs, ME<sub>α-COMe</sub>s and ME<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s. The influences of MEs, ME<sub>α-COMe</sub>s and ME<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s are subtle. A better understanding of organometallic bond energies can suggest whether proposed new catalytic systems may work well.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445863","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
Copper(II) complex of pentadentate N5 ligand as catalyst for2-aminophenol oxidation 作为 2-氨基苯酚氧化催化剂的五价 N5 配体铜(II)络合物
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-09-12 DOI: 10.1016/j.ica.2024.122372

Exploring the catalytic activity of the copper(II) complex of pentadentate ligand in oxidizing o-aminophenol (OAP) has not been extensively studied. To scrutinize the least explored domain, we synthesized and characterized the copper(II) complex of pentadentate ligand, 3-(bis(pyridin-2-ylmethyl)amino)-N-(quinolin-8-yl)propanamide. Further, the complex was allowed to react with OAP to form 2-aminophenoxazin-3-one (APX) via oxidative coupling reaction, the resultant product is a functional analogue of phenoxazinone synthase (PHS), an active enzyme, relevant to the industrial production of a widely recognized antibiotic called Actinomycin D. Furthermore, kinetic studies were performed to comprehend the path of the reaction which unveiled the formation of the complex-substrate adduct. It is worth noticing that the complex displayed an impressive turnover number of 6.4 × 104 h−1 under atmospheric conditions in methanol. To the best of our knowledge, the present complex is the first copper(II) complex with pentadentate N5 ligand showing PHS mimicking catalytic activity.

关于五价配体铜(II)配合物在氧化邻氨基苯酚(OAP)中的催化活性的探索尚未得到广泛研究。为了仔细研究这一研究最少的领域,我们合成并表征了五价配体 3-(双(吡啶-2-基甲基)氨基)-N-(喹啉-8-基)丙酰胺的铜(II)配合物。此外,还进行了动力学研究,以了解反应的路径,从而揭示络合物-底物加合物的形成过程。值得注意的是,在大气条件下,该复合物在甲醇中的转化率高达 6.4 × 104 h-1。据我们所知,本复合物是第一个具有五价 N5 配体的铜(II)复合物,具有模仿 PHS 的催化活性。
{"title":"Copper(II) complex of pentadentate N5 ligand as catalyst for2-aminophenol oxidation","authors":"","doi":"10.1016/j.ica.2024.122372","DOIUrl":"10.1016/j.ica.2024.122372","url":null,"abstract":"<div><p>Exploring the catalytic activity of the copper(II) complex of pentadentate ligand in oxidizing <em>o</em>-aminophenol (OAP) has not been extensively studied. To scrutinize the least explored domain, we synthesized and characterized the copper(II) complex of pentadentate ligand, 3-(bis(pyridin-2-ylmethyl)amino)-<em>N</em>-(quinolin-8-yl)propanamide. Further, the complex was allowed to react with OAP to form 2-aminophenoxazin-3-one (APX) via oxidative coupling reaction, the resultant product is a functional analogue of phenoxazinone synthase (PHS), an active enzyme, relevant to the industrial production of a widely recognized antibiotic called Actinomycin D. Furthermore, kinetic studies were performed to comprehend the path of the reaction which unveiled the formation of the complex-substrate adduct. It is worth noticing that the complex displayed an impressive turnover number of 6.4 × 10<sup>4</sup> h<sup>−1</sup> under atmospheric conditions in methanol. To the best of our knowledge, the present complex is the first copper(II) complex with pentadentate N5 ligand showing PHS mimicking catalytic activity.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004638/pdfft?md5=36a8b4128b39de5f7a96cc38a417b674&pid=1-s2.0-S0020169324004638-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Inorganica Chimica Acta
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