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Mono-, di-, and trinuclear cobalt(III) complexes with a H2salpn derivative: metal-assisted ligand transformation leading to the unusual formation of 2H-1,3-benzoxazine ring 含H2salpn衍生物的单核、二核和三核钴(III)配合物:金属辅助配体转化导致不寻常的2h -1,3-苯并恶嗪环的形成
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-14 DOI: 10.1016/j.ica.2026.123083
Seema Nagarajan, Ankit Kumar Srivastava, Samudranil Pal
Reaction of Co(ClO4)2·6H2O, N,N′-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (H2L, where 2 Hs stand for the two phenolic protons) and NEt3 in 1:1:2 mol ratio in acetonitrile under aerobic conditions at 298 K produced [Co22-OH)2(L)2] (1), [Co(L′)2]ClO4 (2), and [Co33-O)(μ2-OH)(μ2-L)2(L′)]ClO4·2H2O (3·2H2O) (HL′ = N-salicylidene-2-methyl-2-(2H-1,3-benzoxazine-2-yl)propylamine, where H denotes the phenolic proton). All three complexes were characterized by ESI-MS, IR and UV–Vis spectroscopic, and X-ray crystallographic measurements. The physical characteristics and the X-ray structures are consistent with the molecular formulas and +3 oxidation state of the metal centers in all three complexes. The structures revealed that one of the two 2-((methyleneimino)methyl)phenol (–CH2N=CHC6H4OH) arms of H2L is changed to 2H-1,3-benzoxazine, leading to the formation of HL′. The ON2O-donor (L)2− occupies one axial and three meridional positions in both 1 and 3·2H2O, while the transformed ligand (L′) acts as a facially coordinating N2O-donor in both 2 and 3·2H2O. The metal centers are in distorted octahedral N2O4 coordination spheres in 1 and 3·2H2O. In contrast, the metal center has a distorted octahedral N4O2 coordination environment in 2. Based on EPR and ESI-MS studies, a mechanism for the observed ligand transformation via metal-assisted alkyl C–H activation followed by C–O bond formation involving a radical intermediate has been proposed.
Co(ClO4)2·6H2O, N,N ' -双(水杨基)-2,2-二甲基-1,3-丙二胺(H2L,其中2H代表两个酚类质子)与NEt3在298 K的好氧条件下以1:1:2 摩尔比反应生成[Co2(μ2-OH)2(L)2] (1), [Co(L ')2]ClO4(2)和[Co3(μ3-O)(μ2-OH)(μ2-L)2(L ‘)]ClO4·2H2O(3·2H2O) (HL ’ = N-水杨基-2-甲基-2-(2h -1,3-苯并杂嗪-2-基)丙胺,H表示酚类质子)。通过ESI-MS、IR和UV-Vis光谱以及x射线晶体学测量对这三种配合物进行了表征。这三种配合物的物理特征和x射线结构与分子式和金属中心的+3氧化态一致。结果表明,H2L的两个2-(亚甲基亚胺)甲基苯酚(- ch2n =CHC6H4OH)臂中的一个变为2h -1,3-苯并恶嗪,形成HL '。on20 -供体(L)2−在1和3·2H2O中占据一个轴向和三个子午线位置,而转化的配体(L’)−在2和3·2H2O中作为一个面配位的n20 -供体。金属中心在1和3·2H2O中呈畸变八面体N2O4配位球。相反,金属中心在2中具有扭曲的八面体N4O2配位环境。基于EPR和ESI-MS研究,提出了一种观察到的配体转化机制,通过金属辅助烷基C-H活化,然后形成涉及自由基中间体的C-O键。
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引用次数: 0
Experimental and DFT study of the bis-Schiff base N,N′-pyridyl-imine ligand as a probe for Hg2+ in DMSO solvent 双希夫碱N,N ' -吡啶亚胺配体在DMSO溶剂中作为Hg2+探针的实验和DFT研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-14 DOI: 10.1016/j.ica.2026.123080
Sondos A.J. Almahmoud , Md. Mohon Shek , Soad S. Alzahrani , Md. Shakil Hossen , Wisnu Arfian A. Sudjarwo , Asma Rshood Alshraim , A.F.M. Motiur Rahman , Abdullah Alodhayb , Shofiur Rahman , Paris E. Georghiou
Mercury contamination in the natural environment and from industrial products and their by-products poses well-documented public health concerns due to its toxicity, persistence, and bioaccumulation. The present study reports on the synthesis and properties of the symmetrical bis-Schiff base ligand, (1E,1E′)-N,N′-(1,4-phenylene)bis(1-(pyridin-2-yl)methanimine) (“NPIL”), which exhibits a rapid and distinct colorless to dark yellow colorimetric change upon complexation with Hg2+ ions in DMSO media, enabling naked-eye detection. UV–Vis titration in DMSO revealed a strong association constant (Ka = 4.8 × 103 M−1) and a low detection limit (LOD) of 0.027 μM and a quantification limit (LOQ) of 23 μM. The LOD is substantially below Health Canada's recommended value of 2.48 μM. The coordination of Hg2+ via the ligand's imine and pyridine nitrogen atoms, as ascertained from 1H NMR titration experiments in DMSO‑d6 suggested 2:1, 2:2, and 4:4 metal-to-ligand stoichiometries. Density functional theory (DFT) calculations were performed for several conformations of the host ligand NPIL and its complexes with HgCl₂ in DMSO. The binding interaction energies showed that of four possible “A-D" conformations of NPIL examined, a 2:1 HgCl2 complex with the All-cis D conformation (−113.30 kJ·mol−1) is more stable than the 2:1 HgCl2 complex with the Cis-trans-cis C conformation (−111.50 kJ·mol−1) due to strong ligand-to-metal charge transfer and stabilizing noncovalent interactions. The combination of high sensitivity, selective optical response, and its simple synthesis makes NPIL a suitable candidate as a cost-effective UV–vis probe for mercury ion detection.
由于汞的毒性、持久性和生物蓄积性,自然环境和工业产品及其副产品中的汞污染引起了充分记录的公共卫生问题。本研究报道了对称双希夫碱配体(1E,1E′)-N,N′-(1,4-苯基)双(1-(吡啶-2-基)甲亚胺)(“NPIL”)的合成和性质,该配体在DMSO介质中与Hg2+离子络合后表现出快速而明显的无色到深黄色的显色变化,可以用肉眼检测。DMSO的紫外-可见滴定显示出较强的关联常数(Ka = 4.8 × 103 M−1),低检出限(LOD)为0.027 μM,定量限(LOQ)为23 μM。LOD远低于加拿大卫生部的推荐值2.48 μM。Hg2+通过配体的亚胺和吡啶氮原子的配位,通过DMSO - d6的1H NMR滴定实验确定了2:1,2:2和4:4的金属-配体化学计量。对宿主配体NPIL及其与HgCl 2配合物在DMSO中的几种构象进行了密度泛函理论(DFT)计算。结合能表明,在NPIL的四种可能的“a -D”构象中,具有全顺式D构象(- 113.30 kJ·mol−1)的2:1 HgCl2配合物比具有顺-反式C构象(- 111.50 kJ·mol−1)的2:1 HgCl2配合物更稳定,这是由于配体与金属之间的强电荷转移和稳定的非共价相互作用。高灵敏度、选择性光学响应和简单的合成使NPIL成为一种适合用于汞离子检测的低成本紫外-可见探针。
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引用次数: 0
Regioselective hydroboration of alkenes by metal-organic framework confined mononuclear bipyridyl–iron hydride catalyst 金属-有机框架约束单核联吡啶-氢化铁催化烯烃的区域选择性硼化反应
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-14 DOI: 10.1016/j.ica.2026.123082
Aditya Kumar , Rahul Kalita , Poorvi Gupta, Bharti Rana, Manav Chauhan, Kuntal Manna
Hydroboration of alkenes offers an atom-economical method for producing alkylboronates, which are valuable intermediates in organic synthesis. We report the development of a single-site iron(II) hydride species supported by bipyridine-functionalized UiO metal-organic frameworks (bpy-UiO-FeH2), which serves as a highly active heterogeneous catalyst for selective anti-Markovnikov hydroboration of alkenes. The catalyst yields anti-Markovnikov boronate ester products with up to 94% selectivity at 60 °C and exhibits broad substrate compatibility, accommodating alkenes with diverse substitution patterns and functional groups. In comparison to its homogeneous counterpart (bipyridine–Fe), bpy-UiO-FeH2 demonstrates superior activity, enhanced selectivity, and excellent recyclability due to the active site isolation of the mononuclear bpy–FeH2 species within the MOF scaffold, which suppresses intermolecular decomposition pathways. Detailed mechanistic studies on styrene hydroboration, supported by control experiments, spectroscopic analyses, and computational investigations, revealed key insights into the catalytic pathway. This study underscores the potential of MOF-supported earth-abundant metal catalysts for environmentally friendly organic transformations.
烷基硼酸盐是有机合成中有价值的中间体,烯烃的硼氢化反应是一种原子经济的制备方法。我们报道了一种由联吡啶功能化的UiO金属有机框架(bpyy -UiO- feh2)支持的单位点铁(II)氢化物的发展,它作为一种高活性的非均相催化剂,用于选择性抗马尔可夫尼科夫硼化烯烃。该催化剂在60°C下可产生选择性高达94%的反马尔可夫尼科夫硼酸酯产物,并具有广泛的底物相容性,可容纳具有不同取代模式和官能团的烯烃。与其同质对应物(联吡啶- fe)相比,bpy-UiO-FeH2表现出更强的活性、更强的选择性和良好的可回收性,这是由于MOF支架内单个核bpy-FeH2物种的活性位点分离,抑制了分子间分解途径。在控制实验、光谱分析和计算研究的支持下,对苯乙烯氢化硼的详细机理进行了研究,揭示了催化途径的关键见解。这项研究强调了mof支持的土丰金属催化剂在环境友好型有机转化中的潜力。
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引用次数: 0
Theranostics of folic acid conjugated cu on Te nanocomposite: Fluorescence sensing, imaging and selective cytotoxicity towards HeLa cells1 叶酸偶联铜纳米复合材料的治疗:荧光传感、成像和对HeLa细胞的选择性细胞毒性[j]
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-10 DOI: 10.1016/j.ica.2026.123076
Debashree Das , Sampurna Bhattacharya , Shalmali Basu , Saptydeep Das , Ujjal Das , David J. Morgan , Kamalika Sen
A novel folic acid-conjugated composite nanoparticle containing Cu on TeO2 (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 103 cells/mL. XPS analyses confirmed the transformation of Cu2+ to Cu0, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC50 of 15 μg/mL. A moderate DNA binding affinity (Kd = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.
通过绿色合成途径,制备了一种新型的含Cu - TeO2的叶酸共轭复合纳米颗粒(FA-NC),用于肿瘤靶向治疗。该纳米复合材料具有较强的荧光特性,能够灵敏地检测叶酸受体阳性HeLa细胞,检测限为1.82 × 103个细胞/mL。XPS分析证实了Cu2+转化为Cu0,拉曼光谱分析证实了叶酸表面修饰成功。纳米复合材料显示了HeLa细胞在HaCaT细胞上的选择性成像,证实了受体特异性靶向。FA-NC对HeLa细胞具有抗增殖活性,IC50为15 μg/mL。中等的DNA结合亲和力(Kd = 69.2 μM)表明凹槽结合相互作用。这些结果强调FA-NC是一种具有成本效益、生物相容性和双重功能的纳米材料,可用于叶酸受体阳性癌细胞的同时成像和治疗。
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引用次数: 0
Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects Ru(II) -芳烃化学中的酰基硫脲配体:配位模式、结构见解、溶剂和pH效应
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-10 DOI: 10.1016/j.ica.2026.123077
Amir Karim , Rahime Eshaghi Malekshah , Najeeb Ullah , Sodio C.N. Hsu
Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion via the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound via (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.
酰基硫脲配体因其结构的多功能性和丰富的配位化学而引起了人们的极大关注,这是由于在其框架内存在硬(N,O)和软(S)给体原子。在有机钌(II)配合物中,这些配体主要通过硫羰基硫以单齿方式配位,特别是在非极性或中极性溶剂中。然而,在极性质子或碱性条件下,由于酰胺部分的去质子化,涉及(N,S)或(O,S)供体集的双齿配位变得有利。在Ru(II) -芳烃酰基硫脲配合物中,具有一级硫酰胺功能的配体优先采用(N,S)双齿配位模式,而含有二级硫酰胺部分的配体主要表现为(O,S)双齿配位模式。通过特别设计的酰基硫脲配体得到双核Ru(II) -芳烃配合物,其中一个Ru中心通过(S,N)螯合模式配位,而第二个Ru中心通过(O,S)螯合模式结合。这种配位模式的多样性强调了酰基硫脲配体的结构适应性,并支持它们在设计用于催化、材料开发和生物无机化学的功能金属配合物方面的广泛适用性。本文综述了用于制备酰基硫脲配体的一般合成方法,并评估了它们在有机钌配合物中的配位行为和结合模式。本文还综述了配体设计、溶剂极性、反应pH和硫酰胺取代模式对Ru(II)配合物中酰基硫脲配体配位行为的影响。
{"title":"Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects","authors":"Amir Karim ,&nbsp;Rahime Eshaghi Malekshah ,&nbsp;Najeeb Ullah ,&nbsp;Sodio C.N. Hsu","doi":"10.1016/j.ica.2026.123077","DOIUrl":"10.1016/j.ica.2026.123077","url":null,"abstract":"<div><div>Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion <em>via</em> the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound <em>via</em> (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123077"},"PeriodicalIF":3.2,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035754","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
Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice 在石墨烯薄膜上沉积锰MOF用于饮用水和果汁中百草枯的有效电化学检测
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-08 DOI: 10.1016/j.ica.2026.123067
Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang
Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM−1 cm−2. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.
百草枯(PQ)是一种有毒的杀虫剂,即使浓度很低,但它被广泛用作农业除草剂。因此,我们通过饮食不断接触到PQ。因此,有必要在食用前对蔬菜和水果中的该杀虫剂进行定量和定性监测。本文采用一步溶剂热法在高导电石墨烯薄膜(GRF)上生长锰金属有机骨架(Mn-MOFs),合成了一种柔性杂化膜,并首次探索了将其作为电化学检测PQ的传感器电极。用不同的形态学和光谱技术对制备的杂化膜进行了表征。采用不同的电化学方法对Mn-MOF/GRF杂化物的电催化性能进行了评价。Mn-MOF@GRF传感器电极具有良好的PQ检测性能,线性检测范围为0.05 ~ 350 μM,灵敏度为63.44 μA μM−1 cm−2。该传感器电极的检测下限(LOD)和定量下限(LOQ)分别为2.9 nM和9.03 nM,具有良好的重现性和抗干扰性。在实时样品分析中,混合传感器电极对苹果汁和手泵饮用水样品的回收率为96.4-105.4%,与HPLC法对相同样品的回收率为95.2-105.7%接近。因此,这种柔性传感电极有潜力用于制造便携式电化学生物传感器,用于监测食品中的百草枯。
{"title":"Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice","authors":"Baban Dey ,&nbsp;SK Safdar Hossain ,&nbsp;Hayat Khan ,&nbsp;Akbar Niaz ,&nbsp;Arup Choudhury ,&nbsp;Duck-Joo Yang","doi":"10.1016/j.ica.2026.123067","DOIUrl":"10.1016/j.ica.2026.123067","url":null,"abstract":"<div><div>Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM<sup>−1</sup> cm<sup>−2</sup>. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123067"},"PeriodicalIF":3.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950249","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 structural analysis of heteroleptic molybdenum(VI) complexes with N-alkoxy carboxamide ligands n -烷氧基羧酰胺杂电性钼配合物的合成及结构分析
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-06 DOI: 10.1016/j.ica.2026.123066
Sung Kwang Lee , Dongseong Park , Heenang Choi , Ji Yeon Ryu , Seung Uk Son , Bo Keun Park , Taek-Mo Chung
Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced N-alkoxy carboxamide ligands to bis(tert-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(NtBu)2(mdpa)2 (mdpaH = N-methoxy-2,2-dimethylpropanamide) (1), Mo(NtBu)2(edpa)2 (edpaH = N-ethoxy-2,2-dimethylpropanamide) (2), Mo(NtBu)2(empa)2 (empaH = N-ethoxy-2-methylpropanamide) (3), Mo(NtBu)2(mpa)2 (mpaH = N-methoxypropanamide) (4), Mo(NtBu)2(bdpa)2 (bdpaH = N-tert-butoxy-2,2-dimethylpropanamide) (5) and Mo(NtBu)2(etfa)2 (etfaH = N-ethoxy-2,2,2-trifluoroacetamide) (6) were synthesized by double substitution reactions of Mo(NtBu)2Cl2(DME) (DME = 1,2-dimethoxyethane) and sodium salt of N-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex 1 was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex 1 exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex 4 was measured by vapor pressure measurement and it indicates that complex 4 has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.
双(亚胺)钼(VI)配合物由于其结构稳定性和易挥发性,被研究作为钼薄膜沉积过程中的前驱物。在本研究中,我们将n -烷氧基羧酰胺配体引入到双(叔丁基氨基)钼配合物上,合成了新型杂电性钼(VI)配合物。配合物Mo(NtBu)2(mdpa)2 (mdpaH = n -甲氧基-2,2-二甲基丙酰胺)(1)、Mo(NtBu)2(edpa)2 (edpaH = n -乙氧基-2,2-二甲基丙酰胺)(2)、Mo(NtBu)2(empa)2 (empaH = n -乙氧基-2-甲基丙酰胺)(3)、Mo(NtBu)2(mpa)2 (mpaH = n -甲氧基丙酰胺)(4)、以Mo(NtBu)2Cl2(DME) (DME = 1,2-二甲氧基乙烷)与n -烷氧基羧酰胺钠盐在己烷中进行双取代反应,合成Mo(NtBu)2(bdpa)2 (bdpaH = n -叔丁基-2,2-二甲基丙酰胺)(5)和Mo(NtBu)2(etfa)2 (etfaH = n -乙氧基-2,2,2-三氟乙酰胺)(6)。然后用核磁共振光谱(NMR)、傅里叶变换红外光谱(FT-IR)和元素分析(EA)对所有新配合物进行了表征。为确定配合物1的精确结构,采用单晶x射线衍射(SC-XRD)对其进行了分析。x射线单晶学研究表明,配合物1存在于扭曲的八面体分子几何结构中,其中钼与相应配体的N和O原子结合。用热重分析(TGA)研究了配合物的热性能。结果表明,在分析范围内,所有配合物均发生汽化和分解。通过蒸汽压测定了配合物4的挥发性,表明配合物4具有足够的挥发性(1 Torr @ 74.8°C),适合气相沉积过程。
{"title":"Synthesis and structural analysis of heteroleptic molybdenum(VI) complexes with N-alkoxy carboxamide ligands","authors":"Sung Kwang Lee ,&nbsp;Dongseong Park ,&nbsp;Heenang Choi ,&nbsp;Ji Yeon Ryu ,&nbsp;Seung Uk Son ,&nbsp;Bo Keun Park ,&nbsp;Taek-Mo Chung","doi":"10.1016/j.ica.2026.123066","DOIUrl":"10.1016/j.ica.2026.123066","url":null,"abstract":"<div><div>Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced <em>N</em>-alkoxy carboxamide ligands to bis(<em>tert</em>-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(N<sup>t</sup>Bu)<sub>2</sub>(mdpa)<sub>2</sub> (mdpaH = <em>N</em>-methoxy-2,2-dimethylpropanamide) (<strong>1</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(edpa)<sub>2</sub> (edpaH = <em>N</em>-ethoxy-2,2-dimethylpropanamide) (<strong>2</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(empa)<sub>2</sub> (empaH = <em>N</em>-ethoxy-2-methylpropanamide) (<strong>3</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(mpa)<sub>2</sub> (mpaH = <em>N</em>-methoxypropanamide) (<strong>4</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(bdpa)<sub>2</sub> (bdpaH = <em>N</em>-<em>tert</em>-butoxy-2,2-dimethylpropanamide) (<strong>5</strong>) and Mo(N<sup>t</sup>Bu)<sub>2</sub>(etfa)<sub>2</sub> (etfaH = <em>N</em>-ethoxy-2,2,2-trifluoroacetamide) (<strong>6</strong>) were synthesized by double substitution reactions of Mo(N<sup>t</sup>Bu)<sub>2</sub>Cl<sub>2</sub>(DME) (DME = 1,2-dimethoxyethane) and sodium salt of <em>N</em>-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex <strong>1</strong> was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex <strong>1</strong> exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex <strong>4</strong> was measured by vapor pressure measurement and it indicates that complex <strong>4</strong> has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123066"},"PeriodicalIF":3.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939889","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
Binding and stabilizing effects of chiral Ru(II) polypyridyl complexes Δ- and Λ-[Ru(bpy)2(bidppz)]2+ toward RNA triplex poly(U-A*U) 手性Ru(II)多吡啶基配合物Δ-和Λ-[Ru(bpy)2(bidppz)]2+对RNA三聚体(U- a *U)的结合及稳定作用
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-05 DOI: 10.1016/j.ica.2026.123065
Yanqin Shen , Lifeng Tan
To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)2(bidppz)]2+ (Δ/Λ-1; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[d]imidazol-2-yl)dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-1 exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-1. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-1 interacted more effectively with RNA triplex than Δ-1. Thermal melting studies revealed that Δ-1 and Λ-1 significantly stabilized the third-strand of RNA triplex, with Λ-1 exhibiting a slightly stronger stabilizing effect than Δ-1. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.
为了研究Ru-dppz衍生的手性钌(II)多吡啶配合物对RNA三络合物的相互作用和稳定作用,合成了一对光学纯对映体Δ/Λ-[Ru(bpy)2(bidppz)]2+ (Δ/Λ-1; bpy = 2,2 ' -联吡啶,bidppz = 11-(1h -苯并[d]咪唑-2-基)双吡啶[3,2-a:2 ',3 ' -c]非那嗪)。对映体与RNA三聚体(U- a *U)(“-”表示Watson-Crick碱基配对,“”表示Hoogsteen碱基配对)的结合特性通过波谱和流体动力学技术进行了研究。吸收分光光度测定结果表明,Λ-1对三聚体(U- a *U)的结合亲和力略高于Δ-1。发射光谱和粘度测量进一步支持了这一观察结果,证实Λ-1与RNA三联体的相互作用比Δ-1更有效。热熔研究表明,Δ-1和Λ-1显著稳定了RNA三联体的第三链,其中Λ-1的稳定作用略强于Δ-1。RNA三联体采用右手a型螺旋结构。因此,由于优越的空间相容性,Δ-enantiomer通常比Λ-enantiomer具有更高的结合亲和力。这项研究强调,当与RNA三联体相互作用时,并非所有对映体都坚持Δ-preference,这表明Ru-dppz衍生物作为RNA三联体稳定剂是理解金属配合物如何设计靶向RNA结构的重要一步。
{"title":"Binding and stabilizing effects of chiral Ru(II) polypyridyl complexes Δ- and Λ-[Ru(bpy)2(bidppz)]2+ toward RNA triplex poly(U-A*U)","authors":"Yanqin Shen ,&nbsp;Lifeng Tan","doi":"10.1016/j.ica.2026.123065","DOIUrl":"10.1016/j.ica.2026.123065","url":null,"abstract":"<div><div>To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)<sub>2</sub>(bidppz)]<sup>2+</sup> (Δ/Λ-<strong>1</strong>; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[<em>d</em>]imidazol-2-<em>yl)</em>dipyrido[3,2-<em>a</em>:2′,3′-<em>c</em>]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-<strong>1</strong> exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-<strong>1</strong>. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-<strong>1</strong> interacted more effectively with RNA triplex than Δ-<strong>1</strong>. Thermal melting studies revealed that Δ-<strong>1</strong> and Λ-<strong>1</strong> significantly stabilized the third-strand of RNA triplex, with Λ-<strong>1</strong> exhibiting a slightly stronger stabilizing effect than Δ-<strong>1</strong>. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123065"},"PeriodicalIF":3.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950250","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
Noncovalent interaction-driven supramolecular organization in cobalt(III) azide complexes: Experimental and theoretical insights 叠氮化钴配合物中非共价相互作用驱动的超分子组织:实验和理论见解
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-03 DOI: 10.1016/j.ica.2025.123057
Susovan Bera , Antonio Frontera , Shouvik Chattopadhyay
Three cobalt complexes, [CoIII(HL1)2(N3)2]ClO4 (1), [CoIII(L2)(HL2)(N3)]ClO4 (2) and [CoIII(L3)(bzan)(N3)] (3), where HL1 = 2-(3-(cyclohexylamino)propyliminomethyl)-6-ethoxyphenol, HL2 = 2-(2-(dimethylamino)ethyliminomethyl)-6-methoxyphenol, HL3 = 2-((2-(diethylamino)ethylimino)methyl)-4,6-dichlorophenol and Hbzan = 1-benzoylacetone, were synthesized and characterized. Complexes 1 and 2 crystallize as cationic mononuclear units with perchlorate counter ions, while complex 3 is a neutral mononuclear species. Structural analyses reveal diverse supramolecular features, including hydrogen bonding, CH⋯O, and CH⋯π interactions. To better understand the role of these noncovalent interactions in directing crystal packing, density functional theory (DFT) calculations were performed. In complex 1, QTAIM analysis was applied to assess the strength and topology of hydrogen-bonded chains and cation⋯anion⋯cation motifs involving perchlorate. In complexes 2 and 3, supramolecular dimerization energies were evaluated, revealing dominant CH⋯O and CH⋯π interactions, respectively. Notably, in complex 3, a comparative study between conventional CH⋯π(arene) and unconventional CH⋯π(azide) interactions was carried out using a model system. Molecular electrostatic potential (MEP) surfaces and QTAIM analyses further support the presence and strength of these interactions. This combined experimental–theoretical approach highlights the structural relevance of weak forces in shaping the solid-state organization of Co(III) complexes.
合成了3种钴配合物[CoIII(HL1)2(N3)2]ClO4 (1), [CoIII(L2)(HL2)(N3)]ClO4(2)和[CoIII(L3)(bzan)(N3)](3),其中HL1 = 2-(3-(环己基氨基)丙基氨基)-6-乙氧基苯酚,HL2 = 2-(2-(二乙基氨基)乙基氨基)甲基)-4,6-二氯苯酚和Hbzan = 1-苯甲酰丙酮。配合物1和2与高氯酸盐反离子结晶为阳离子单核单位,而配合物3是中性单核物质。结构分析揭示了不同的超分子特征,包括氢键、CH⋯O和CH⋯π相互作用。为了更好地理解这些非共价相互作用在指导晶体堆积中的作用,进行了密度泛函理论(DFT)计算。在配合物1中,QTAIM分析用于评估氢键链的强度和拓扑结构以及涉及高氯酸盐的阳离子⋯阴离子⋯阳离子基元。在配合物2和3中,超分子二聚化能被评估,分别揭示了主要的CH⋯O和CH⋯π相互作用。值得注意的是,在络合物3中,使用模型系统进行了常规CH⋯π(芳烃)和非常规CH⋯π(叠氮化物)相互作用的比较研究。分子静电势(MEP)表面和QTAIM分析进一步支持了这些相互作用的存在和强度。这种结合实验-理论的方法强调了弱力在形成Co(III)配合物的固态组织中的结构相关性。
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引用次数: 0
Low-spin Fe(III)/Co(II) mixed-ligand benzimidazole/Schiff-base complexes: structural, electronic reactivity, and correlated antimicrobial and anti-inflammatory bioactivity against FabH-CoA and COX-2 低自旋Fe(III)/Co(II)混合配体苯并咪唑/希夫碱配合物:结构、电子反应性以及对FabH-CoA和COX-2的相关抗菌和抗炎生物活性
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-03 DOI: 10.1016/j.ica.2026.123061
Saeed S. Samman , Aly Abdou , Abdulrahman A. Alsimaree , Munirah M. Al-Rooqi , Abdulaziz M. Almohyawi , Rabab.S. Jassas , Ziad Moussa , Sultan I. Alkubaysi , A. Timoumi , Saleh A. Ahmed
Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H2O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm2 mol−1 (FeSBMB) and 9.86 S cm2 mol−1 (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against K. pneumoniae (25.0 ± 0.09 mm), while showing the highest activity index against E. coli (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against E. coli, 23.6 ± 0.11 mm against C. albicans, and 13.8 ± 0.20 mm against A. flavus. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (K. pneumoniae), 17.2 ± 0.12 mm (E. coli), 21.8 ± 0.09 mm (C. albicans), and 12.9 ± 0.14 mm (A. flavus). Anti-inflammatory IC50 values were 21.26 μg mL−1 (FeSBMB) and 25.08 μg mL−1 (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL−1) and MB (55.28 μg mL−1). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV−1), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV−1). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.
以1-异丙基- 1h -苯并咪唑-2-乙醛(MB)和1-([(4-甲基苯基)亚胺]甲基萘-2-醇(SB)为原料合成了两种新型低自旋铁(III)和钴(II)混合配体配合物FeSBMB [Fe(MB)(SB)(Cl) 2]和CoSBMB [Co(MB)(SB)(Cl)(H2O)]。通过CHN分析、FT-IR、UV-Vis、质谱、磁化率、电导率、TG/DTG和Job’s法确定了其结构和八面体几何形状。电导率为10.15 S cm2 mol−1 (FeSBMB)和9.86 S cm2 mol−1 (CoSBMB),证实了它们的非电解性质。磁矩为1.79 B.M. (FeSBMB)和1.83 B.M. (CoSBMB)符合低自旋八面体构型。FeSBMB的抑菌活性最强,对肺炎克雷伯菌的抑制区最大(25.0±0.09 mm),对大肠杆菌的抑菌活性指数最高(97.51%),与参比药的抑菌活性指数为19.6±0.11 mm,对大肠杆菌的抑菌活性指数最高。对白色念珠菌为23.6±0.11 mm,对黄芽孢杆菌为13.8±0.20 mm。CoSBMB活性较低,分别为肺炎克雷伯菌(22.5±0.08 mm)、大肠杆菌(17.2±0.12 mm)、白色念珠菌(21.8±0.09 mm)和黄芽胞杆菌(12.9±0.14 mm)。抗炎IC50值分别为21.26 μg mL−1 (FeSBMB)和25.08 μg mL−1 (CoSBMB),均优于非配位体SB (54.50 μg mL−1)和MB (55.28 μg mL−1)。DFT计算证实了八面体结构,结果表明FeSBMB具有最小的HOMO-LUMO间隙(1.47 eV),最低的硬度(0.74 eV)和最高的柔软度(0.68 eV−1),与CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV−1)相比具有更强的反应性。TD-DFT光谱再现了实验紫外-可见跃迁。对接研究表明,FeSBMB和CoSBMB与FabH-CoA(分别为- 8.50和- 8.10 kcal/mol)和COX-2(分别为- 9.90和- 9.50 kcal/mol)有很强的结合,这与它们的抗菌和抗炎活性一致。
{"title":"Low-spin Fe(III)/Co(II) mixed-ligand benzimidazole/Schiff-base complexes: structural, electronic reactivity, and correlated antimicrobial and anti-inflammatory bioactivity against FabH-CoA and COX-2","authors":"Saeed S. Samman ,&nbsp;Aly Abdou ,&nbsp;Abdulrahman A. Alsimaree ,&nbsp;Munirah M. Al-Rooqi ,&nbsp;Abdulaziz M. Almohyawi ,&nbsp;Rabab.S. Jassas ,&nbsp;Ziad Moussa ,&nbsp;Sultan I. Alkubaysi ,&nbsp;A. Timoumi ,&nbsp;Saleh A. Ahmed","doi":"10.1016/j.ica.2026.123061","DOIUrl":"10.1016/j.ica.2026.123061","url":null,"abstract":"<div><div>Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H<sub>2</sub>O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm<sup>2</sup> mol<sup>−1</sup> (FeSBMB) and 9.86 S cm<sup>2</sup> mol<sup>−1</sup> (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against <em>K. pneumoniae</em> (25.0 ± 0.09 mm), while showing the highest activity index against <em>E. coli</em> (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against <em>E. coli</em>, 23.6 ± 0.11 mm against <em>C. albicans</em>, and 13.8 ± 0.20 mm against <em>A. flavus</em>. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (<em>K. pneumoniae</em>), 17.2 ± 0.12 mm (<em>E. coli</em>), 21.8 ± 0.09 mm (<em>C. albicans</em>), and 12.9 ± 0.14 mm (<em>A. flavus</em>). Anti-inflammatory IC<sub>50</sub> values were 21.26 μg mL<sup>−1</sup> (FeSBMB) and 25.08 μg mL<sup>−1</sup> (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL<sup>−1</sup>) and MB (55.28 μg mL<sup>−1</sup>). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV<sup>−1</sup>), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV<sup>−1</sup>). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123061"},"PeriodicalIF":3.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939817","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
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Inorganica Chimica Acta
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