Pub Date : 2025-11-25DOI: 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.
{"title":"Pyrazolylimine complexes Ni(II) – Precatalysts for the synthesis branched polyethylene","authors":"Daniele Saracheno , Anton O. Vikhrov , Roman V. Rassokhin , Vladislav A. Tuskaev , Svetlana Ch. Gagieva , Svetlana A. Aksenova-Soloveva , Mikhail I. Buzin , Boris M. Bulychev","doi":"10.1016/j.ica.2025.123002","DOIUrl":"10.1016/j.ica.2025.123002","url":null,"abstract":"<div><div>Seven new and one previously described pyrazolylimine complex NiBr<sub>2</sub> 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).</div><div>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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123002"},"PeriodicalIF":3.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683084","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}
Pub Date : 2025-11-24DOI: 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.
{"title":"Cyclopentadienyl Ir(III) complexes as photosensitizers for antibacterial photodynamic therapy: experimental and computational insights","authors":"Arif Ali Mandal , Saurav Kumar , Apurba Mandal , Prodyut Dhar , Samya Banerjee","doi":"10.1016/j.ica.2025.123003","DOIUrl":"10.1016/j.ica.2025.123003","url":null,"abstract":"<div><div>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 <em>viz.</em>, [(Cp*)Ir(phen)Cl]PF<sub>6</sub> (<strong>Ir1</strong>), [(Cp*)Ir(phen-NO<sub>2</sub>)Cl]PF<sub>6</sub> (<strong>Ir2</strong>), and [(Cp*)Ir(phen-NH<sub>2</sub>)Cl)]PF<sub>6</sub> (<strong>Ir3</strong>) (where cyclopentadienyl = Cp*, 1,10 phenanthroline = phen, 5-nitro-1,10-phenanthroline = phen-NO<sub>2</sub>, 5-amino-1,10-phenanthroline = phen-NH<sub>2</sub>). The X-ray crystal structure of <strong>Ir3</strong> revealed a half-sandwich pseudo-octahedral geometry of the complexes. An absorption band at the <em>ca.</em> 325–400 nm region and photostability supported the potential application of <strong>Ir1</strong>-<strong>Ir3</strong> in antibacterial photodynamic therapy. Photophysical studies revealed that <strong>Ir1</strong>-<strong>Ir3</strong> generated singlet oxygen (<sup>1</sup>O<sub>2</sub>) (Φ<sub>Δ</sub> = 0.14–0.11) and photo-catalytically oxidize NADH (TOF = 48.3 ± 3.2 to 54.3 ± 4.2 h<sup>−1</sup>). DFT/TD-DFT studies revealed that <strong>Ir1-Ir3</strong> efficiently generate singlet oxygen <em>via</em> the type II pathway. Moreover, <strong>Ir2</strong> showed the highest efficacy as compared to <strong>Ir1</strong> and <strong>Ir3</strong> against both <em>Escherichia coli</em> (Gram-(−)) and <em>Staphylococcus aureus</em> (Gram-(+)) bacteria with MIC values of 0.5 μg/mL upon visible light (400–700 nm, 10 J cm<sup>−2</sup>) exposure. Notably, <strong>Ir1</strong>-<strong>Ir3</strong> showed no bacterial inhibition activity under dark conditions. Additionally, molecular docking studies were performed against DNA gyrase B (PDB ID: <span><span>4uro</span><svg><path></path></svg></span>), PBP2a (PDB ID: <span><span>4CJN</span><svg><path></path></svg></span>) protein, and FabH (PDB ID: <span><span>1EBL</span><svg><path></path></svg></span>) protein to elucidate the binding modes of <strong>Ir1</strong>-<strong>Ir3</strong> 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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 123003"},"PeriodicalIF":3.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621632","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}
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.
{"title":"Iron based metal–organic frameworks MIL-53 (Fe): A comprehensive review on advanced synthesis strategies and photocatalytic energy & environmental applications","authors":"Ugrabadi Sahoo , Samarjit Pattnayak , Shubhalaxmi Choudhury , Pragnyashree Aparajita , Sandip Padhiari , Garudadhwaj Hota","doi":"10.1016/j.ica.2025.123001","DOIUrl":"10.1016/j.ica.2025.123001","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 123001"},"PeriodicalIF":3.2,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621630","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}
Pub Date : 2025-11-13DOI: 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.
{"title":"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","authors":"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","doi":"10.1016/j.ica.2025.122989","DOIUrl":"10.1016/j.ica.2025.122989","url":null,"abstract":"<div><div>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 cm<sup>2</sup> mol<sup>−1</sup>) confirms non-electrolytic behavior. IR spectroscopy reveals coordination via phenolic oxygen (<em>ν</em>(OH) shift to 3461–3466 cm<sup>−1</sup>) and azomethine nitrogen (ν(C=N) shift to 1613–1616 cm<sup>−1</sup>), with new M–O/N bands (508–528 cm<sup>−1</sup>). UV–Vis spectra and magnetic moments (μ<sub>eff</sub> = 1.81 B.M. for MnRC; 3.74 B.M. for CrRC) support octahedral geometry, with MnRC adopting a low-spin d<sup>5</sup> configuration. Mass spectrometry (<em>m</em>/<em>z</em> 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<sup>−1</sup>), 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 <em>S. aureus</em> TyrRS via H-bonding, electrostatic, and hydrophobic interactions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 122989"},"PeriodicalIF":3.2,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578050","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}
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.
{"title":"Preparation, crystal structures and photophysical properties of two green upconversion photoluminescence holmium mercury complexes","authors":"Hao-Dong Liu, Long-Hua Zeng, Xi-Yu Shao, Cheng Liu, 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}
Pub Date : 2025-11-06DOI: 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.
{"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 , Rajat Kumar Roy , Abhilash Pandey , Srishti Dutta , Meman Sahu , Uttam Kumar Das , Annpurna Sahu , Dharmendra Kumar Parihar , 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}
Pub Date : 2025-11-05DOI: 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.
{"title":"Synthesis and structures of Eu(II) complexes with anionic perfluoro-2-mercaptobenzothiazolate and macrocyclic ligands","authors":"Anton N. Ostrosablin , Vasily A. Ilichev , Anton F. Rogozhin , Olga V. Kuznetsova , Pavel V. Dorovatovskii , Roman V. Rumyantcev , Georgy K. Fukin , 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}
Pub Date : 2025-11-04DOI: 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.
{"title":"A multifaceted study of three Cu(II) Schiff base complexes as urease inhibitors: Derived from experimental and computational approaches","authors":"Pengxiao Guo , Rongqi Wang , Yadong Zhou , Chaochuang Yin , Yizhu Lei , Yinyan Wang , Kang Chen , Li Sun , Ziao Zong , Hu Wang","doi":"10.1016/j.ica.2025.122986","DOIUrl":"10.1016/j.ica.2025.122986","url":null,"abstract":"<div><div>Herein, we explore the development of three copper(II) Schiff base complexes (Cu-SBC, <strong>C1</strong>-<strong>C3</strong>) 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. <strong>C1</strong> and <strong>C2</strong> display four-coordinate distorted square planar geometries, while <strong>C3</strong> adopts a five-coordinate distorted square pyramidal configuration. The biological evaluation revealed that <strong>C1</strong> demonstrated a markedly enhanced UA inhibitory activity compared to the standard reference acetohydroxamic acid (IC<sub>50</sub>: 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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122986"},"PeriodicalIF":3.2,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145525955","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}
Pub Date : 2025-11-04DOI: 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.
{"title":"Synthesis, characterization, electrochemical, and theoretical investigation of nitro-substituted salophen Schiff base complexes","authors":"Hadi Kargar , Maciej Kubicki , Mehdi Fallah-Mehrjardi , Hamid Reza Zare-Mehrjardi , Fatemeh Abyar , Khurram Shahzad Munawar , Muhammad Ashfaq","doi":"10.1016/j.ica.2025.122984","DOIUrl":"10.1016/j.ica.2025.122984","url":null,"abstract":"<div><div>A series of nitro-substituted salophen Schiff base complexes, <strong>NiL</strong>, <strong>CuL</strong>, and <strong>ZnL</strong>, were synthesized and characterized using elemental analysis and various spectroscopic techniques. Single-crystal X-ray diffraction of <strong>NiL</strong> confirmed tetradentate coordination of the ligand to the nickel center, forming a slightly distorted square planar geometry stabilized by extensive intermolecular interactions such as C<img>H⋯O, π⋯π, π⋯Ni, C<img>H⋯π, and N<img>O⋯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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122984"},"PeriodicalIF":3.2,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463709","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}
Pub Date : 2025-11-03DOI: 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.
{"title":"Imidazole-based chemosensors: A promising approach for trace copper(II) monitoring","authors":"Md. Zafer Alam , Md. Sameer Ahmed , Humaira Parveen , Sayeed Mukhtar , Salman A. Khan","doi":"10.1016/j.ica.2025.122983","DOIUrl":"10.1016/j.ica.2025.122983","url":null,"abstract":"<div><div>Copper(II) ion (Cu<sup>2+</sup>) 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 Cu<sup>2+</sup> 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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 122983"},"PeriodicalIF":3.2,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578048","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}