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Pyrazolylimine complexes Ni(II) – Precatalysts for the synthesis branched polyethylene 吡唑亚胺配合物Ni(II) -合成支化聚乙烯的预催化剂
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-25 DOI: 10.1016/j.ica.2025.123002
Daniele Saracheno , Anton O. Vikhrov , Roman V. Rassokhin , Vladislav A. Tuskaev , Svetlana Ch. Gagieva , Svetlana A. Aksenova-Soloveva , Mikhail I. Buzin , Boris M. Bulychev
Seven new and one previously described pyrazolylimine complex NiBr2 with aryl substituents exhibiting different electronic effects on the imine carbon atom were synthesized and characterized. It was shown that the obtained compounds are effective catalysts for ethylene polymerization in the presence of diethylaluminum chloride (DEAC).
The influence of the electronic properties of the R substituents on the catalytic performance of the complexes was systematically investigated. A clear correlation between ligand electron-donating or -withdrawing character and both polymer molecular weight and catalytic activity was observed, providing insight into the electronic factors governing the efficiency of these nickel-based systems.
合成了7个新的和1个已知的具有芳基取代基的吡唑亚胺配合物NiBr2,它们在亚胺碳原子上具有不同的电子效应。结果表明,所得化合物是二乙基氯化铝(DEAC)存在下乙烯聚合的有效催化剂。系统地研究了R取代基的电子性质对配合物催化性能的影响。观察到配体的供电子或吸电子特性与聚合物分子量和催化活性之间存在明显的相关性,从而深入了解控制这些镍基体系效率的电子因素。
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引用次数: 0
Cyclopentadienyl Ir(III) complexes as photosensitizers for antibacterial photodynamic therapy: experimental and computational insights 环戊二烯基Ir(III)配合物作为抗菌光动力治疗的光敏剂:实验和计算见解
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-24 DOI: 10.1016/j.ica.2025.123003
Arif Ali Mandal , Saurav Kumar , Apurba Mandal , Prodyut Dhar , Samya Banerjee
Bacterial infections are one of the serious global health concerns; new strategies to prevent bacterial infections are urgently needed. Light-responsive metal-based drugs can combat bacterial infections. Herein, we report three half-sandwich organoiridium(III)-based complexes viz., [(Cp*)Ir(phen)Cl]PF6 (Ir1), [(Cp*)Ir(phen-NO2)Cl]PF6 (Ir2), and [(Cp*)Ir(phen-NH2)Cl)]PF6 (Ir3) (where cyclopentadienyl = Cp*, 1,10 phenanthroline = phen, 5-nitro-1,10-phenanthroline = phen-NO2, 5-amino-1,10-phenanthroline = phen-NH2). The X-ray crystal structure of Ir3 revealed a half-sandwich pseudo-octahedral geometry of the complexes. An absorption band at the ca. 325–400 nm region and photostability supported the potential application of Ir1-Ir3 in antibacterial photodynamic therapy. Photophysical studies revealed that Ir1-Ir3 generated singlet oxygen (1O2) (ΦΔ = 0.14–0.11) and photo-catalytically oxidize NADH (TOF = 48.3 ± 3.2 to 54.3 ± 4.2 h−1). DFT/TD-DFT studies revealed that Ir1-Ir3 efficiently generate singlet oxygen via the type II pathway. Moreover, Ir2 showed the highest efficacy as compared to Ir1 and Ir3 against both Escherichia coli (Gram-(−)) and Staphylococcus aureus (Gram-(+)) bacteria with MIC values of 0.5 μg/mL upon visible light (400–700 nm, 10 J cm−2) exposure. Notably, Ir1-Ir3 showed no bacterial inhibition activity under dark conditions. Additionally, molecular docking studies were performed against DNA gyrase B (PDB ID: 4uro), PBP2a (PDB ID: 4CJN) protein, and FabH (PDB ID: 1EBL) protein to elucidate the binding modes of Ir1-Ir3 within the active sites, revealing crucial interactions that showed their significant activity against bacteria. Overall, in this work, we have demonstrated the promising potential of Ir(III) complexes as effective antibacterial agents under the influence of visible light.
细菌感染是严重的全球卫生问题之一;现在迫切需要预防细菌感染的新策略。光反应性金属药物可以对抗细菌感染。本文报道了三种半夹层有机铱(III)基配合物,即[(Cp*)Ir(phen)Cl]PF6 (Ir1), [(Cp*)Ir(phenn - no2)Cl]PF6 (Ir2)和[(Cp*)Ir(phenn - nh2)Cl)]PF6 (Ir3)(其中环pentadienyl = Cp*, 1,10-菲罗啉= phen, 5-硝基-1,10-菲罗啉= pheno - no2, 5-氨基-1,10-菲罗啉= phenn - no2, 5-氨基-1,10-菲罗啉= phenn - nh2))。Ir3的x射线晶体结构显示了配合物的半夹心伪八面体几何结构。Ir1-Ir3在约325-400 nm区域的吸收带和光稳定性支持了其在抗菌光动力治疗中的潜在应用。光物理研究表明,Ir1-Ir3生成单线态氧(10o2) (ΦΔ = 0.14-0.11),并光催化氧化NADH (TOF = 48.3±3.2 ~ 54.3±4.2 h−1)。DFT/TD-DFT研究表明Ir1-Ir3通过II型途径有效地产生单线态氧。此外,在可见光(400-700 nm, 10 J cm−2)下,Ir2对大肠杆菌(革兰氏-(−))和金黄色葡萄球菌(革兰氏-(+))的MIC值为0.5 μg/mL,与Ir1和Ir3相比,Ir2的效果最好。值得注意的是,Ir1-Ir3在黑暗条件下没有细菌抑制活性。此外,我们对DNA旋切酶B (PDB ID: 4uro)、PBP2a (PDB ID: 4CJN)蛋白和FabH (PDB ID: 1EBL)蛋白进行了分子对接研究,以阐明Ir1-Ir3在活性位点内的结合模式,揭示了它们具有显著抗细菌活性的关键相互作用。总的来说,在这项工作中,我们已经证明了Ir(III)配合物在可见光影响下作为有效抗菌剂的潜力。
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引用次数: 0
Iron based metal–organic frameworks MIL-53 (Fe): A comprehensive review on advanced synthesis strategies and photocatalytic energy & environmental applications 铁基金属有机骨架MIL-53 (Fe):先进合成策略及其光催化能源与环境应用综述
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-21 DOI: 10.1016/j.ica.2025.123001
Ugrabadi Sahoo , Samarjit Pattnayak , Shubhalaxmi Choudhury , Pragnyashree Aparajita , Sandip Padhiari , Garudadhwaj Hota
Metal–organic frameworks (MOFs) have transfigured the landscape of advanced materials, with MIL-53 (Fe) a flexible, porous structure comprising iron salts and terephthalic acidemerging as a standout candidate for next-generation applications. Renowned for its “breathing” behavior and tunable structural properties, MIL-53 (Fe) has demonstrated exceptional potential in both adsorption and photocatalysis. Early research focused on developing crystalline MOFs with optimal surface areas and porosity using diverse metal-linker combinations, but current efforts are shifting toward innovative synthesis routes and exploring their versatile functionalities. This review critically examines the state-of-the-art strategies for MIL-53 (Fe) synthesis, such as electrochemical, solvothermal, and microwave-assisted methods, evaluating their effectiveness and limitations. We emphasize the unique optoelectronic properties, high chemical stability, and adjustable band gap of MIL-53 (Fe), which collectively confer superior photocatalytic effectiveness in processes like oxygen evolution, hydrogen production, and visible-light-driven pollutant degradation. By synthesizing recent advancements, we address pivotal design considerations, discuss the impact of structural modifications, and elucidate the fundamental factors influencing MIL-53 (Fe) photoactivity. Special emphasis is placed on environmental remediation and sustainable energy applications. Future research directions are proposed, including novel functionalization strategies and heterojunction fabrication, to supplementary enhance the photocatalytic activity of MIL-53 (Fe)-based materials. This comprehensive review aims to serve as a valuable guide for researchers, fostering the continued development and application of MIL-53 (Fe) MOFs in the pursuit of greener, more sustainable technologies.
金属有机框架(mof)已经改变了先进材料的格局,MIL-53 (Fe)是一种由铁盐和对苯二甲酸盐组成的柔性多孔结构,是下一代应用的杰出候选者。MIL-53 (Fe)以其“呼吸”行为和可调节的结构特性而闻名,在吸附和光催化方面都表现出了非凡的潜力。早期的研究主要集中在使用不同的金属连接剂组合开发具有最佳表面积和孔隙度的晶体mof,但目前的努力正在转向创新的合成路线并探索其多功能。这篇综述严格审查了MIL-53 (Fe)合成的最新策略,如电化学、溶剂热和微波辅助方法,评估了它们的有效性和局限性。我们强调了MIL-53 (Fe)独特的光电特性、高化学稳定性和可调节的带隙,这些特性共同赋予了MIL-53 (Fe)在析氧、制氢和可见光驱动污染物降解等过程中的优越光催化效果。通过对最新进展的综合,我们解决了关键的设计问题,讨论了结构修饰的影响,并阐明了影响MIL-53 (Fe)光活性的基本因素。特别强调环境补救和可持续能源的应用。提出了未来的研究方向,包括新的功能化策略和异质结的制备,以补充提高MIL-53 (Fe)基材料的光催化活性。本文旨在为研究人员提供有价值的指导,促进MIL-53 (Fe) mof的持续开发和应用,以追求更绿色,更可持续的技术。
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引用次数: 0
Synthesis, Structural Characterization and Biological Activity of Mn(II) and Cr(III) Complexes with a 3-(3,4-dichlorobenzenyl)-1-(4-((2-hydroxybenzylidene)amino)benzenyl)-2-propen-1-one schiff base ligand: Unraveling Electronic Factors of Bioactivity 3-(3,4-二氯苯基)-1-(4-(2-羟基苄基)氨基苯基)-2-丙烯-1- 1希夫碱配体Mn(II)和Cr(III)配合物的合成、结构表征和生物活性:揭示生物活性的电子因素
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-13 DOI: 10.1016/j.ica.2025.122989
Antar A. Abdelhamid , Majidah Alsaeedi , Anas Alfarsi , Manal M. Alzahrani , Obaid A. Alharbi , Mansour Alsarrani , Raafat A. El-Eisawy , Abdullah Ahmed A. Alghamdi , Aly Abdou
The bidentate Schiff base ligand RC, synthesized through sequential condensation of p-aminoacetophenone with 3,4-dichlorobenzaldehyde followed by salicylaldehyde, coordinates to Mn(II) and Cr(III) ions to form neutral octahedral complexes [Mn(RC)₂(H₂O)₂] and [Cr(RC)₂(H₂O)(Cl)]. Comprehensive characterization confirms their structures and 1:2 metal:ligand stoichiometry. Molar conductivity (8.68–8.77 μS cm2 mol−1) confirms non-electrolytic behavior. IR spectroscopy reveals coordination via phenolic oxygen (ν(OH) shift to 3461–3466 cm−1) and azomethine nitrogen (ν(C=N) shift to 1613–1616 cm−1), with new M–O/N bands (508–528 cm−1). UV–Vis spectra and magnetic moments (μeff = 1.81 B.M. for MnRC; 3.74 B.M. for CrRC) support octahedral geometry, with MnRC adopting a low-spin d5 configuration. Mass spectrometry (m/z 883.241 for MnRC; 893.775 for CrRC) and elemental analysis validate molecular integrity. DFT calculations highlight MnRC's superior reactivity: smallest HOMO-LUMO gap (2.36 eV), highest softness (0.42 eV−1), and strongest electrophilicity (7.02 eV). Antimicrobial assays show MnRC > CrRC > RC in potency, with inhibition zones up to 20 mm and activity ≤85 %. Molecular docking corroborates enhanced bioactivity, with MnRC exhibiting the highest binding affinity (−8.60 kcal/mol) against S. aureus TyrRS via H-bonding, electrostatic, and hydrophobic interactions.
通过对氨基苯乙酮与3,4-二氯苯甲醛和水杨醛的顺序缩合,合成了双齿希夫碱配体RC,并与Mn(II)和Cr(III)离子配位形成中性的八面体配合物[Mn(RC)₂(H₂O)₂]和[Cr(RC)₂(H₂O) Cl]。综合表征证实了它们的结构和1:2金属:配体的化学计量。摩尔电导率(8.68-8.77 μS cm2 mol−1)证实了非电解行为。红外光谱揭示了酚氧(ν(OH)移位到3461 ~ 3466 cm−1)和亚甲基氮(ν(C=N)移位到1613 ~ 1616 cm−1)的配位,具有新的M-O /N波段(508 ~ 528 cm−1)。MnRC的紫外可见光谱和磁矩(μeff = 1.81 B.M., CrRC为3.74 B.M.)支持八面体几何结构,且MnRC采用低自旋d5构型。质谱分析(MnRC为m/z 883.241; CrRC为893.775)和元素分析验证了分子的完整性。DFT计算突出了MnRC优越的反应性:最小的HOMO-LUMO间隙(2.36 eV),最高的柔软度(0.42 eV−1)和最强的亲电性(7.02 eV)。抗菌试验显示MnRC >; CrRC >; RC效价高,抑制区达20 mm,活性≤85%。分子对接证实了增强的生物活性,MnRC通过h键、静电和疏水相互作用对金黄色葡萄球菌TyrRS表现出最高的结合亲和力(−8.60 kcal/mol)。
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引用次数: 0
Preparation, crystal structures and photophysical properties of two green upconversion photoluminescence holmium mercury complexes 两种绿色上转换光致发光钬汞配合物的制备、晶体结构及光物理性质
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-07 DOI: 10.1016/j.ica.2025.122975
Hao-Dong Liu, Long-Hua Zeng, Xi-Yu Shao, Cheng Liu, Wen-Tong Chen
Two novel holmium mercury isonicotinic acid/nicotinic acid materials, [Ho(HIA)3(H2O)2]2n·3n(HgBr4)·4nH2O (1) (HIA = isonicotinic acid) and [Ho(HNA)3(H2O)2]2n·3n(HgCl4)·4nH2O (2) (HNA = nicotinic acid), were obtained through hydrothermal reactions, and their structural features were analyzed by single – crystal X – ray diffraction. Both of these complexes display a one – dimensional (1 – D) chain – like framework. The lanthanide ions within them are in eight – coordination configurations, and the mercury ions are in four – coordination patterns. Semiconductor bandgaps were ascertained from solid-state UV/Vis diffuse reflectance measurements, yielding values of 3.21 eV for complex 1 and 2.98 eV for complex 2. Solid-state sample-based photoluminescence investigations indicate that both complexes produce green upconverting photoluminescence. The underlying cause of this photoluminescence is the characteristic emission due to the 4f electron intrashell transition (5S2 → 5I8) in Ho3+ ions existing in both complexes. The Commission Internationale de l'Éclairage (CIE) color space positions compounds 1 and 2 at (0.6679, 0.3318) and (0.2446, 0.7376), with associated correlated color temperatures measured as 6497 K and 6814 K.
通过水热反应制得[Ho(HIA)3(H2O)2]2n·3n(HgBr4)·4nH2O (1) (HIA =异烟酸)和[Ho(HNA)3(H2O)2]2n·3n(HgCl4)·4nH2O (2) (HNA =烟酸)两种新型钬汞异烟酸/烟酸材料,并通过单晶X射线衍射分析了它们的结构特征。这两种配合物都显示一维(1 - D)链状框架。其中的镧系离子呈八配位构型,汞离子呈四配位构型。通过固体UV/Vis漫反射测量确定了半导体带隙,配合物1的产率为3.21 eV,配合物2的产率为2.98 eV。基于固态样品的光致发光研究表明,这两种配合物都能产生绿色上转换光致发光。这种光致发光的根本原因是由于两种配合物中存在的Ho3+离子的4f电子壳内跃迁(5S2→5I8)而产生的特征发射。国际委员会Éclairage (CIE)颜色空间将化合物1和2定位在(0.6679,0.3318)和(0.2446,0.7376),相关色温分别为6497 K和6814 K。
{"title":"Preparation, crystal structures and photophysical properties of two green upconversion photoluminescence holmium mercury complexes","authors":"Hao-Dong Liu,&nbsp;Long-Hua Zeng,&nbsp;Xi-Yu Shao,&nbsp;Cheng Liu,&nbsp;Wen-Tong Chen","doi":"10.1016/j.ica.2025.122975","DOIUrl":"10.1016/j.ica.2025.122975","url":null,"abstract":"<div><div>Two novel holmium mercury isonicotinic acid/nicotinic acid materials, [Ho(HIA)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>2<em>n</em></sub>·3<em>n</em>(HgBr<sub>4</sub>)·4<em>n</em>H<sub>2</sub>O (<strong>1</strong>) (HIA = isonicotinic acid) and [Ho(HNA)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>2<em>n</em></sub>·3<em>n</em>(HgCl<sub>4</sub>)·4<em>n</em>H<sub>2</sub>O (<strong>2</strong>) (HNA = nicotinic acid), were obtained through hydrothermal reactions, and their structural features were analyzed by single – crystal X – ray diffraction. Both of these complexes display a one – dimensional (1 – D) chain – like framework. The lanthanide ions within them are in eight – coordination configurations, and the mercury ions are in four – coordination patterns. Semiconductor bandgaps were ascertained from solid-state UV/Vis diffuse reflectance measurements, yielding values of 3.21 eV for complex <strong>1</strong> and 2.98 eV for complex <strong>2</strong>. Solid-state sample-based photoluminescence investigations indicate that both complexes produce green upconverting photoluminescence. The underlying cause of this photoluminescence is the characteristic emission due to the 4f electron intrashell transition (<sup>5</sup><em>S</em><sub>2</sub> → <sup>5</sup><em>I</em><sub>8</sub>) in Ho<sup>3+</sup> ions existing in both complexes. The Commission Internationale de l'Éclairage (CIE) color space positions compounds <strong>1</strong> and <strong>2</strong> at (0.6679, 0.3318) and (0.2446, 0.7376), with associated correlated color temperatures measured as 6497 K and 6814 K.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122975"},"PeriodicalIF":3.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145525956","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
2-(4-Nitrophenyl)-4,5-diphenyl-1H-imidazole based selective and sensitive chemosensor for fluorescent colorimetric detection of Fe3+ and colorimetric detection of S2− ions 基于2-(4-硝基苯基)-4,5-二苯基- 1h -咪唑的选择性灵敏化学传感器,用于荧光比色法检测Fe3+和S2−离子
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-06 DOI: 10.1016/j.ica.2025.122988
Devanand Sahu , Rajat Kumar Roy , Abhilash Pandey , Srishti Dutta , Meman Sahu , Uttam Kumar Das , Annpurna Sahu , Dharmendra Kumar Parihar , Goutam Kumar Patra
Here in, we describe the synthesis, characterisation and properties of optical sensing of 2-(4-Nitrophenyl)-4,5-diphenyl 1H-imidazole (L). While L showed a discernible color change from light yellow to orange and change in UV–Vis absorption spectra on the addition of S2−, across the wide range of tested anions, it also showed a selective sensitivity towards the Fe3+ ion over other tested metal ions through an emission quenching effect and a change in UV–Vis absorption spectra. Fe3+ has a fluorometric detection limit of 4.7 × 10−7 M, whereas S2− and Fe3+ have absorption detection limits of 2.3 × 10−8 M and 5.8 × 10−6 M, respectively. Compared to the WHO drinking water guidelines, these readings were substantially lower. A 1:1 stoichiometric complexation between L and Fe3+ and a 2:1 stoichiometric complexation between L and S2− (deprotonation from the –NH site of the receptor L) have been established using the Job's plot analysis, the ESI-MS spectra, and the 1H NMR data. The detection of Fe3+ and S2− ions in real samples, logic gate design, colorimetric test kit tests, and the preparation of antimicrobial agents can all benefit from the usage of L.
本文介绍了2-(4-硝基苯基)-4,5-二苯基1h -咪唑(L)的合成、表征和光学传感性能。随着S2−的加入,L的颜色从浅黄色变为橙色,紫外-可见吸收光谱也发生了变化。在广泛的阴离子测试范围内,L对Fe3+离子表现出选择性敏感性,通过发射猝灭效应和紫外-可见吸收光谱的变化。Fe3+的荧光检测限为4.7 × 10−7 M,而S2−和Fe3+的吸收检测限分别为2.3 × 10−8 M和5.8 × 10−6 M。与世界卫生组织的饮用水指南相比,这些读数要低得多。利用Job’s plot分析、ESI-MS谱和1H NMR数据,建立了L与Fe3+之间1:1的化学计量络合和L与S2−之间2:1的化学计量络合(从受体L的-NH位点脱质子)。实际样品中Fe3+和S2−离子的检测、逻辑门设计、比色试剂盒测试以及抗菌剂的制备都可以受益于L的使用。
{"title":"2-(4-Nitrophenyl)-4,5-diphenyl-1H-imidazole based selective and sensitive chemosensor for fluorescent colorimetric detection of Fe3+ and colorimetric detection of S2− ions","authors":"Devanand Sahu ,&nbsp;Rajat Kumar Roy ,&nbsp;Abhilash Pandey ,&nbsp;Srishti Dutta ,&nbsp;Meman Sahu ,&nbsp;Uttam Kumar Das ,&nbsp;Annpurna Sahu ,&nbsp;Dharmendra Kumar Parihar ,&nbsp;Goutam Kumar Patra","doi":"10.1016/j.ica.2025.122988","DOIUrl":"10.1016/j.ica.2025.122988","url":null,"abstract":"<div><div>Here in, we describe the synthesis, characterisation and properties of optical sensing of 2-(4-Nitrophenyl)-4,5-diphenyl 1<em>H</em>-imidazole (<strong>L</strong>). While <strong>L</strong> showed a discernible color change from light yellow to orange and change in UV–Vis absorption spectra on the addition of S<sup>2−</sup>, across the wide range of tested anions, it also showed a selective sensitivity towards the Fe<sup>3+</sup> ion over other tested metal ions through an emission quenching effect and a change in UV–Vis absorption spectra. Fe<sup>3+</sup> has a fluorometric detection limit of 4.7 × 10<sup>−7</sup> M, whereas S<sup>2−</sup> and Fe<sup>3+</sup> have absorption detection limits of 2.3 × 10<sup>−8</sup> M and 5.8 × 10<sup>−6</sup> M, respectively. Compared to the WHO drinking water guidelines, these readings were substantially lower. A 1:1 stoichiometric complexation between <strong>L</strong> and Fe<sup>3+</sup> and a 2:1 stoichiometric complexation between <strong>L</strong> and S<sup>2−</sup> (deprotonation from the –NH site of the receptor <strong>L</strong>) have been established using the Job's plot analysis, the ESI-MS spectra, and the <sup>1</sup>H NMR data. The detection of Fe<sup>3+</sup> and S<sup>2−</sup> ions in real samples, logic gate design, colorimetric test kit tests, and the preparation of antimicrobial agents can all benefit from the usage of <strong>L</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 122988"},"PeriodicalIF":3.2,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500416","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 and structures of Eu(II) complexes with anionic perfluoro-2-mercaptobenzothiazolate and macrocyclic ligands 阴离子全氟-2-巯基苯并噻唑酸和大环配体的Eu(II)配合物的合成和结构
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-05 DOI: 10.1016/j.ica.2025.122987
Anton N. Ostrosablin , Vasily A. Ilichev , Anton F. Rogozhin , Olga V. Kuznetsova , Pavel V. Dorovatovskii , Roman V. Rumyantcev , Georgy K. Fukin , Mikhail N. Bochkarev
Complexes of divalent europium with perfluoro-2-mercaptobenzothiazolate (mbtF) and a set of macrocyclic ligands - 18-dbc-6, 18-crown-6, [2.2]cryptand and [2.2.2]cryptand, were synthesized. Accordingly X-ray data, applying of 18-dbc-6 yields complex 1 with a composition Eu(mbtF)2(18-dbc-6) in which 18-dbc-6 acts as hexadentate ligand and one of mbtF ligands is chelately coordinated, while the other exhibits monodentate coordination via the thiolate sulfur. In complexes with 18-crown-6 and [2.2]cryptand macrocyclic ligands with general formulas Eu(mbtF)2(18-crown-6) (2) and Eu(mbtF)2([2.2]cryptand) (3), respectively, show similar hexadentate coordination of macrocyclic ligands but only monodentate coordination mode of mbtF ligands to europium. Additionally, the molecular structure of complex 3 is stabilized by intramolecular N-H…N interactions of [2.2]cryptand and mbtF ligands. A complex with [2.2.2]cryptand ligand of a composition Eu(mbtF)2([2.2.2]cryptand) (4) does not give crystals, however it reacts with copper(I) iodide yielding a highly luminescent europium diiodide [EuI([2.2.2]cryptand)]I (5) which contains a complex cation [EuI([2.2.2]cryptand)]+ where the macrocyclic ligand exhibits octadentate coordination mode.
合成了二价铕与全氟-2-巯基苯并噻唑啉(mbtF)和一组大环配体- 18-dbc- 6,18 -冠-6、[2.2]隐式和[2.2.2]隐式的配合物。根据x射线数据,应用18bc -6得到的配合物1具有Eu(mbtF)2(18bc -6)的组合物,其中18bc -6作为六齿配体,其中一个mbtF配体是螯合配体,而另一个mbtF配体通过硫酸硫表现为单齿配体。在具有通式的18-crown-6和[2.2]密码大环配体配合物中,Eu(mbtF)2(18-crown-6)(2)和Eu(mbtF)2([2.2]密码大环配体)(3)显示出类似的大环配体的六齿配位模式,但mbtF配体与铕只有单齿配位模式。此外,配合物3的分子结构是由[2.2]密码体和mbtF配体的分子内N- h…N相互作用稳定的。与[2.2.2]cryptand配体组成的Eu(mbtF)2([2.2.2]cryptand)(4)的配合物不会产生晶体,但它与铜(I)碘化反应产生高度发光的二碘化铕[EuI([2.2.2]cryptand)]I(5),其中包含一个配合阳离子[EuI([2.2.2]cryptand)]+,其中大环配体表现出八齿配位模式。
{"title":"Synthesis and structures of Eu(II) complexes with anionic perfluoro-2-mercaptobenzothiazolate and macrocyclic ligands","authors":"Anton N. Ostrosablin ,&nbsp;Vasily A. Ilichev ,&nbsp;Anton F. Rogozhin ,&nbsp;Olga V. Kuznetsova ,&nbsp;Pavel V. Dorovatovskii ,&nbsp;Roman V. Rumyantcev ,&nbsp;Georgy K. Fukin ,&nbsp;Mikhail N. Bochkarev","doi":"10.1016/j.ica.2025.122987","DOIUrl":"10.1016/j.ica.2025.122987","url":null,"abstract":"<div><div>Complexes of divalent europium with perfluoro-2-mercaptobenzothiazolate (mbt<sup>F</sup>) and a set of macrocyclic ligands - 18-dbc-6, 18-crown-6, [2.2]cryptand and [2.2.2]cryptand, were synthesized. Accordingly X-ray data, applying of 18-dbc-6 yields complex <strong>1</strong> with a composition Eu(mbt<sup>F</sup>)<sub>2</sub>(18-dbc-6) in which 18-dbc-6 acts as hexadentate ligand and one of mbt<sup>F</sup> ligands is chelately coordinated, while the other exhibits monodentate coordination via the thiolate sulfur. In complexes with 18-crown-6 and [2.2]cryptand macrocyclic ligands with general formulas Eu(mbt<sup>F</sup>)<sub>2</sub>(18-crown-6) (<strong>2</strong>) and Eu(mbt<sup>F</sup>)<sub>2</sub>([2.2]cryptand) (<strong>3</strong>), respectively, show similar hexadentate coordination of macrocyclic ligands but only monodentate coordination mode of mbt<sup>F</sup> ligands to europium. Additionally, the molecular structure of complex <strong>3</strong> is stabilized by intramolecular N-H…N interactions of [2.2]cryptand and mbt<sup>F</sup> ligands. A complex with [2.2.2]cryptand ligand of a composition Eu(mbt<sup>F</sup>)<sub>2</sub>([2.2.2]cryptand) (<strong>4</strong>) does not give crystals, however it reacts with copper(I) iodide yielding a highly luminescent europium diiodide [EuI([2.2.2]cryptand)]I (<strong>5</strong>) which contains a complex cation [EuI([2.2.2]cryptand)]<sup>+</sup> where the macrocyclic ligand exhibits octadentate coordination mode.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122987"},"PeriodicalIF":3.2,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463714","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
A multifaceted study of three Cu(II) Schiff base complexes as urease inhibitors: Derived from experimental and computational approaches 三种Cu(II)希夫碱配合物作为脲酶抑制剂的多方面研究:来自实验和计算方法
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-04 DOI: 10.1016/j.ica.2025.122986
Pengxiao Guo , Rongqi Wang , Yadong Zhou , Chaochuang Yin , Yizhu Lei , Yinyan Wang , Kang Chen , Li Sun , Ziao Zong , Hu Wang
Herein, we explore the development of three copper(II) Schiff base complexes (Cu-SBC, C1-C3) aimed at inhibiting urease (UA), achieved through the thoughtful design of ligands. By integrating a fluorinated Schiff base ligand (SBL) with auxiliary ligands—namely, 2-methylimidazole, 2-ethylimidazole, and 6,6′-dimethyl-2,2′-bipyridine—this research systematically examines the impact of steric factors on the inhibition of the UA enzyme. The synthesized complexes underwent comprehensive characterization, including crystallographic analysis. The three synthesized Cu(II) complexes exhibit two distinct coordination geometries dictated by their auxiliary ligands. C1 and C2 display four-coordinate distorted square planar geometries, while C3 adopts a five-coordinate distorted square pyramidal configuration. The biological evaluation revealed that C1 demonstrated a markedly enhanced UA inhibitory activity compared to the standard reference acetohydroxamic acid (IC50: 6.12 ± 0.44 vs. 27.73 ± 2.93 μM). Computational methodologies were employed to complement the experimental investigations, elucidating the molecular underpinnings of the observed activity disparities among the complexes. Consequently, the structure-activity relationship analysis indicates that steric hindrance is crucial in modulating the UA inhibitory activity, providing important perspectives for the development of new UA inhibitors and their potential uses in biomedicine.
在此,我们探索了三种铜(II)希夫碱配合物(Cu-SBC, C1-C3)的开发,旨在抑制脲酶(UA),通过配体的精心设计实现。通过将氟化希夫碱配体(SBL)与辅助配体(即2-甲基咪唑,2 -乙基咪唑和6,6 ' -二甲基-2,2 ' -联吡啶)整合,本研究系统地研究了位阻因子对UA酶抑制的影响。对合成的配合物进行了全面的表征,包括晶体学分析。三种合成的Cu(II)配合物表现出两种不同的配位几何形状,由它们的辅助配体决定。C1和C2为四坐标畸变方形平面几何,C3为五坐标畸变方形锥体构型。生物学评价结果显示,与标准乙酰羟肟酸相比,C1具有明显增强的UA抑制活性(IC50: 6.12±0.44 vs. 27.73±2.93 μM)。采用计算方法来补充实验研究,阐明了观察到的复合物之间活性差异的分子基础。因此,构效关系分析表明,空间位阻在调节UA抑制活性中起着至关重要的作用,为开发新的UA抑制剂及其在生物医学中的潜在应用提供了重要的前景。
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引用次数: 0
Synthesis, characterization, electrochemical, and theoretical investigation of nitro-substituted salophen Schiff base complexes 硝基取代salophen席夫碱配合物的合成、表征、电化学及理论研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-04 DOI: 10.1016/j.ica.2025.122984
Hadi Kargar , Maciej Kubicki , Mehdi Fallah-Mehrjardi , Hamid Reza Zare-Mehrjardi , Fatemeh Abyar , Khurram Shahzad Munawar , Muhammad Ashfaq
A series of nitro-substituted salophen Schiff base complexes, NiL, CuL, and ZnL, were synthesized and characterized using elemental analysis and various spectroscopic techniques. Single-crystal X-ray diffraction of NiL confirmed tetradentate coordination of the ligand to the nickel center, forming a slightly distorted square planar geometry stabilized by extensive intermolecular interactions such as CH⋯O, π⋯π, π⋯Ni, CH⋯π, and NO⋯π, as revealed by Hirshfeld surface analysis. Cyclic voltammetry measurements demonstrated quasi-reversible redox behavior for Ni(II), Cu(II), and Zn(II) complexes, with the Cu(II)/Cu(I) process being the most prominent under physiological pH conditions. Density functional theory (DFT) calculations supported the experimental observations, indicating a smaller HOMO–LUMO energy gap for the synthesized complexes, consistent with their enhanced redox activity. Molecular electrostatic potential (MEP) and natural bond orbital (NBO) analyses revealed significant charge delocalization and strong donor–acceptor interactions, highlighting the mixed ionic–covalent nature of metal–ligand bonding. Overall, experimental and theoretical findings collectively establish the structure–property relationships and electronic characteristics of these nitro-substituted salophen Schiff base complexes.
合成了一系列硝基取代salophen席夫碱配合物NiL、CuL和ZnL,并利用元素分析和各种光谱技术对其进行了表征。如Hirshfeld表面分析所揭示的,NiL的单晶x射线衍射证实了配体与镍中心的四齿配位,形成了一个轻微扭曲的方形平面几何形状,由广泛的分子间相互作用稳定,如CH⋯O, π⋯π, π⋯Ni, CH⋯π和NO⋯π。循环伏安法测量表明,Ni(II)、Cu(II)和Zn(II)配合物具有准可逆氧化还原行为,在生理pH条件下,Cu(II)/Cu(I)过程最为突出。密度泛函理论(DFT)计算支持实验观察,表明合成的配合物具有较小的HOMO-LUMO能隙,与它们增强的氧化还原活性相一致。分子静电电位(MEP)和自然键轨道(NBO)分析揭示了明显的电荷离域和强的供体-受体相互作用,突出了金属-配体键的混合离子-共价性质。总的来说,实验和理论发现共同建立了这些硝基取代的salophen席夫碱配合物的结构-性质关系和电子特性。
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引用次数: 0
Imidazole-based chemosensors: A promising approach for trace copper(II) monitoring 咪唑化学传感器:一种有前途的痕量铜(II)监测方法
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-03 DOI: 10.1016/j.ica.2025.122983
Md. Zafer Alam , Md. Sameer Ahmed , Humaira Parveen , Sayeed Mukhtar , Salman A. Khan
Copper(II) ion (Cu2+) are vital trace elements however, their imbalance is linked to serious health disorders such as Wilson's disease, Menkes syndrome, and neurodegenerative conditions, as well as environmental toxicity. Conventional analytical methods, though precise, are costly and unsuitable for rapid or on-site detection. Imidazole-based chemosensors have emerged as promising alternatives because of their excellent Cu2+ binding capability, tunable photophysical properties, and simple design. Their sensing responses are mediated by chelation-enhanced fluorescence/quenching, intramolecular charge transfer (ICT), and photoinduced electron transfer (PET). Since 2015 imidazole derivatives, such as Schiff base imidazole, bis-imidazole, imidazolium salts, and N-heterocyclic carbine precursors have demonstrated excellent sensitivity, selectivity, and low detection limits, with readout modes spanning colorimetric, fluorescence turn-on/turn-off, and ratiometric sensing. These advances highlight the potential of imidazole-based chemosensors for environmental monitoring, biomedical diagnostics, and cellular imaging, while future developments aim at multifunctional probes with enhanced biocompatibility and real-time applicability.
铜(II)离子(Cu2+)是至关重要的微量元素,然而,它们的失衡与严重的健康疾病有关,如威尔逊病、门克斯综合征、神经退行性疾病,以及环境毒性。传统的分析方法虽然精确,但成本高,不适合快速或现场检测。基于咪唑的化学传感器由于其优异的Cu2+结合能力、可调的光物理性质和简单的设计而成为有前途的替代品。它们的传感响应由螯合增强的荧光/猝灭、分子内电荷转移(ICT)和光诱导电子转移(PET)介导。自2015年以来,咪唑衍生物,如希夫碱咪唑、双咪唑、咪唑盐和n-杂环卡宾前体,具有出色的灵敏度、选择性和低检出限,读出模式涵盖比色法、荧光开/关和比例传感。这些进展突出了咪唑化学传感器在环境监测、生物医学诊断和细胞成像方面的潜力,而未来的发展目标是具有增强生物相容性和实时适用性的多功能探针。
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引用次数: 0
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Inorganica Chimica Acta
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