Pub Date : 2026-04-01Epub Date: 2025-12-27DOI: 10.1016/j.ica.2025.123044
Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang
Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO3)(H2O)]n (1) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm2(OH-bdc)2(H2O)10]·OH-bdc·H2O}n (2) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound 1 features a three dimensional (3D) pillared layer network containing [Tm2(NO3)2]4+ units and 2,5-dtc2− ligands. Compound 2 exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm2(bdc)2(H2O)10]2+ to uncoordinated OH-bdc2− ligands via π···π stacking interactions. The striking feature of compounds 1 and 2 is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds 1 and 2 display antiferromagnetic coupling in the solid state at room temperature.
{"title":"Near-infrared (NIR) luminescence of two Tm(III)-based dicarboxylate coordination polymers","authors":"Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang","doi":"10.1016/j.ica.2025.123044","DOIUrl":"10.1016/j.ica.2025.123044","url":null,"abstract":"<div><div>Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO<sub>3</sub>)(H<sub>2</sub>O)]<sub><em>n</em></sub> (<strong>1</strong>) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm<sub>2</sub>(OH-bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]·OH-bdc·H<sub>2</sub>O}<sub><em>n</em></sub> (<strong>2</strong>) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound <strong>1</strong> features a three dimensional (3D) pillared layer network containing [Tm<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>]<sup>4+</sup> units and 2,5-dtc<sup>2−</sup> ligands. Compound <strong>2</strong> exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm<sub>2</sub>(bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]<sup>2+</sup> to uncoordinated OH-bdc<sup>2−</sup> ligands via <em>π···π</em> stacking interactions. The striking feature of compounds <strong>1</strong> and <strong>2</strong> is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds <strong>1</strong> and <strong>2</strong> display antiferromagnetic coupling in the solid state at room temperature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123044"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939886","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 : 2026-04-01Epub Date: 2025-12-30DOI: 10.1016/j.ica.2025.123058
Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal
The diborane(4) (B2H4) and diborene(2) (B2H2) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the BB bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B2H4 and B2H2 species remains unexplored. Thus the bonding interactions between B2H4/B2H2 and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)2}2{B2H4}] (1) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)2}2B2H2W(CO)4] (2), [{CpW(CO)2}2B2H2Mo(CO)4] (3) and [{CpW(CO)2}2B2H2W(CO)4] (4) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in 1–4 are primarily governed by electrostatic forces (ΔEelec) with notable covalent contributions (ΔEorb). Although 2–4 is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds 2-3 show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in 4 [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound 1. The B2H2 metal-carbonyl bonding interaction is much stronger in 2–3 (∼80–90 kcal/mol higher) compared to 4. Orbital analysis indicates predominant σ-donation from B2H4/B2H2, and in 4, additional π-backdonation from the metal centers strengthens the BB bond.
{"title":"Nature of bonding between B2H4/B2H2 with Homo-/hetero- Di/tri-nuclear-metal-carbonyls","authors":"Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal","doi":"10.1016/j.ica.2025.123058","DOIUrl":"10.1016/j.ica.2025.123058","url":null,"abstract":"<div><div>The diborane(4) (B<sub>2</sub>H<sub>4</sub>) and diborene(2) (B<sub>2</sub>H<sub>2</sub>) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the B<img>B bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B<sub>2</sub>H<sub>4</sub> and B<sub>2</sub>H<sub>2</sub> species remains unexplored. Thus the bonding interactions between B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub> and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)<sub>2</sub>}<sub>2</sub>{B<sub>2</sub>H<sub>4</sub>}] (<strong>1</strong>) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>2</strong>), [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>Mo(CO)<sub>4</sub>] (<strong>3</strong>) and [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>4</strong>) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in <strong>1–4</strong> are primarily governed by electrostatic forces (Δ<em>E</em><sub>elec</sub>) with notable covalent contributions (Δ<em>E</em><sub>orb</sub>). Although <strong>2–4</strong> is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds <strong>2-3</strong> show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in <strong>4</strong> [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound <strong>1</strong>. The B<sub>2</sub>H<sub>2</sub> metal-carbonyl bonding interaction is much stronger in <strong>2</strong>–<strong>3</strong> (∼80–90 kcal/mol higher) compared to <strong>4</strong>. Orbital analysis indicates predominant σ-donation from B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub>, and in <strong>4</strong>, additional π-backdonation from the metal centers strengthens the B<img>B bond.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123058"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939884","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 : 2026-04-01Epub Date: 2025-12-16DOI: 10.1016/j.ica.2025.123041
Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang
Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with D- and L-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(D-val)] and Λ-[Ir(dfppy)₂(L-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(D-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by 1H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.
{"title":"Synthesis, structure and photooxidative dehydrogenation of chiral Ir(III) valine complexes based on precursor [Λ-Ir(dfppy)2(MeCN)2](PF6)","authors":"Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang","doi":"10.1016/j.ica.2025.123041","DOIUrl":"10.1016/j.ica.2025.123041","url":null,"abstract":"<div><div>Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with <em>D</em>- and <em>L</em>-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(<em>D</em>-val)] and Λ-[Ir(dfppy)₂(<em>L</em>-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(<em>D</em>-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by <sup>1</sup>H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123041"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882485","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}
A Schiff base ligand, [4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol], shortly Diformyl Amino Pyridine (DAP), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg2+ binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 108 M−1 and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe DAP was converted into a heterogeneous solid-state material, ZnAl2O4 (ZA) conjugated DAP (ZDAP), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to DAP's quenching, ZDAP exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg2+ binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (ZDAP), causing a bathochromic shift in emission. The observed fluorescence quenching of DAP upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, ZDAP demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.
希夫碱配体[4-甲基-2,6-双((E)-((2-(吡啶-2-基)乙基)亚氨基)甲基)苯酚],简称二甲酰氨基吡啶(DAP),是一种均相探针,并通过不同的光谱技术进行了表征。它的荧光被Hg2+结合猝灭,这一过程受多种非辐射途径的控制,包括光诱导电子转移(PET)和重原子效应,Stern-Volmer常数为8.83 × 108 M−1,检测限为1.35 μM。为了解决可重复使用性和样品基质分离等限制,通过将亚胺配体锚定在ZA尖晶石上,将均相探针DAP转化为非均相固态材料ZnAl2O4 (ZA)共轭DAP (ZDAP)。令人惊讶的是,这种改变从根本上改变了感知机制。与DAP的猝灭相反,ZDAP通过聚集诱导发射(AIE)表现出“开启”反应,其中Hg2+结合限制了分子内运动并增强了荧光。该方法的检出限为1.01 nM。ICP-MS分析证实,使用该传感器处理后,汞几乎完全去除,汞去除率高达98.46%。这两个系统的传感机制已经通过DFT计算和实验技术,如斯特恩-沃尔默分析和时间分辨荧光光谱得到证实。理论计算结果与实验结果非常吻合,能隙从2.28 eV (ZA)减小到2.15 eV (ZDAP),引起发射的深色偏移。所观察到的DAP锚定在ZA上的荧光猝灭是由强配-金属相互作用、电荷转移诱导的非辐射衰变、结构硬化和表面缺陷捕获引起的,与实验(2.93 eV)带隙一致。至关重要的是,ZDAP具有出色的可重复使用性,在螯合剂再生后至少可以保持其传感效率和结构完整性5个循环。这项工作展示了单个希夫基平台如何设计为提供两种互补的传感模式,为汞检测和去除提供敏感,选择性和可持续的解决方案。
{"title":"Concurrent detection and removal of Hg2+ from potable water using ZnAl2O4 modified end off Schiff base ligand: Experimental and theoretical investigation","authors":"Sneha Biswas , Jaydeep Adhikary , Rama Rathi , Sreejeeb Ganguly , Ennio Zangrando , Abhijit Kumar Das","doi":"10.1016/j.ica.2025.123045","DOIUrl":"10.1016/j.ica.2025.123045","url":null,"abstract":"<div><div>A Schiff base ligand, <em>[4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol]</em>, shortly Diformyl Amino Pyridine (<strong>DAP</strong>), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg<sup>2+</sup> binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 10<sup>8</sup> M<sup>−1</sup> and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe <strong>DAP</strong> was converted into a heterogeneous solid-state material, ZnAl<sub>2</sub>O<sub>4</sub> (<strong>ZA</strong>) conjugated <strong>DAP</strong> (<strong>ZDAP</strong>), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to <strong>DAP</strong>'s quenching, <strong>ZDAP</strong> exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg<sup>2+</sup> binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (<strong>ZDAP</strong>), causing a bathochromic shift in emission. The observed fluorescence quenching of <strong>DAP</strong> upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, <strong>ZDAP</strong> demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123045"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839361","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 : 2026-04-01Epub Date: 2025-12-28DOI: 10.1016/j.ica.2025.123047
Islam M. Elnabky , Mohamed M. Aboelnga , Hoda M. El-Gharabawy , Shadia A. Elsayed , Ahmed M. El-Hendawy
Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H2L) with composition [M(L)(X)] (M = Ni or Pd; X = H2O for Ni1, Pd1, or imidazole for Ni2, Pd2) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, 1H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand via deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (Ni2 and Pd1,2) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 104 M−1). Molecular docking further confirmed stable interactions with both biomolecules. The in vitro cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the Pd2 complex exhibited the most potent activity, especially against MDA-MB-231 (IC50 = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The Ni1 and Ni2 complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly Pd2, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.
{"title":"Dehydroacetic acid benzoyl hydrazone complexes of Ni(II) and Pd(II): Synthesis, characterization, computational studies, biomolecular interaction, and dual anticancer–antimicrobial activities","authors":"Islam M. Elnabky , Mohamed M. Aboelnga , Hoda M. El-Gharabawy , Shadia A. Elsayed , Ahmed M. El-Hendawy","doi":"10.1016/j.ica.2025.123047","DOIUrl":"10.1016/j.ica.2025.123047","url":null,"abstract":"<div><div>Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H<sub>2</sub>L) with composition [M(L)(X)] (M = Ni or Pd; X = H<sub>2</sub>O for <strong>Ni1</strong>, <strong>Pd1,</strong> or imidazole for <strong>Ni2</strong>, <strong>Pd2</strong>) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, <sup>1</sup>H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand <em>via</em> deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (<strong>Ni2</strong> and <strong>Pd1,2</strong>) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 10<sup>4</sup> M<sup>−1</sup>). Molecular docking further confirmed stable interactions with both biomolecules. The <em>in vitro</em> cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the <strong>Pd2</strong> complex exhibited the most potent activity, especially against MDA-MB-231 (IC<sub>50</sub> = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The <strong>Ni1</strong> and <strong>Ni2</strong> complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly <strong>Pd2</strong>, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123047"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882484","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 : 2026-04-01Epub Date: 2026-01-03DOI: 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.
{"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 , 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","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":"2026-04-01","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}
Pub Date : 2026-04-01Epub Date: 2026-01-02DOI: 10.1016/j.ica.2026.123062
Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün
A series of morpholine(Morp.)-liganded palladium(II) complexes (1a–c) and triphenylphosphine(PPh3)-liganded palladium(II) complexes (2a–c) bearing 4-fluorobenzyl substituted N-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh3 by ligand exchange method. The new complexes were fully characterized using 1H NMR, 13C NMR, 19F NMR, 31P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes 1a and 2b. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex 1a, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex 1b.
{"title":"New morpholine or triphenylphosphine-liganded palladium(II) N-heterocyclic carbene complexes: Synthesis, characterization, crystal structure, and anticancer activity","authors":"Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün","doi":"10.1016/j.ica.2026.123062","DOIUrl":"10.1016/j.ica.2026.123062","url":null,"abstract":"<div><div>A series of morpholine(Morp.)-liganded palladium(II) complexes (<strong>1a–c</strong>) and triphenylphosphine(PPh<sub>3</sub>)-liganded palladium(II) complexes (<strong>2a–c</strong>) bearing 4-fluorobenzyl substituted <em>N</em>-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh<sub>3</sub> by ligand exchange method. The new complexes were fully characterized using <sup>1</sup>H NMR, <sup>13</sup>C NMR, <sup>19</sup>F NMR, <sup>31</sup>P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes <strong>1a</strong> and <strong>2b</strong>. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex <strong>1a</strong>, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex <strong>1b</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123062"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939948","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}
The addition of calcium phosphate to lead silicate glasses K2O-PbO-SiO2 results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K2O-PbO-SiO2 glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.
{"title":"The phase separation in K2O-PbO-CaO-P2O5-SiO2 glass doped by gold and Eu3+ ions","authors":"Ilya Salakheev , Andrey Drozdov , Maksim Andreev , Claudio Pettinari","doi":"10.1016/j.ica.2025.123048","DOIUrl":"10.1016/j.ica.2025.123048","url":null,"abstract":"<div><div>The addition of calcium phosphate to lead silicate glasses K<sub>2</sub>O-PbO-SiO<sub>2</sub> results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K<sub>2</sub>O-PbO-SiO<sub>2</sub> glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123048"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939885","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}
Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg2+, Cu2+, Zn2+, Ag+, Al3+, Pb2+,Fe3+,Cd2+, Au3+, Pd2+, Ni2+, Cr3+, Ga3+, Zr4+ as well as anions including I−, F− and CN−. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.
{"title":"Thiophene based chemosensors: a comprehensive review on synthesis and detection of cations and anions","authors":"Zuverya Zareen , Aram Rahman , Anzar Jahan , Salahuddin Syed , Mohammad Arifuddin","doi":"10.1016/j.ica.2025.123042","DOIUrl":"10.1016/j.ica.2025.123042","url":null,"abstract":"<div><div>Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ag<sup>+</sup>, Al<sup>3+</sup>, Pb<sup>2+</sup>,Fe<sup>3+</sup>,Cd<sup>2+</sup>, Au<sup>3+</sup>, Pd<sup>2+</sup>, Ni<sup>2+</sup>, Cr<sup>3+</sup>, Ga<sup>3+</sup>, Zr<sup>4+</sup> as well as anions including I<sup>−</sup>, F<sup>−</sup> and CN<sup>−</sup>. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123042"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882482","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 : 2026-04-01Epub Date: 2025-12-07DOI: 10.1016/j.ica.2025.123031
Craig Goodman , Tyler Williams , Abigail G. McNamee , Julia L. Brumaghim
Oxidative DNA damage in cells causes a variety of pathologies including but not limited to cancers, cardiovascular diseases, and neurodegenerative disorders. Fe3+ reduction by NADH is the rate-limiting step in cellular hydroxyl radical generation and damage, but this aspect of the oxidative stress cycle is little explored. We established a rate law for the NADH-Fe system in vitro that indicates the Fe3+ reduction rate depends primarily on NADH concentration, indicating that NADH may be a critical participant in cellular oxidative stress. Kinetic experiments using ferene established that the overall stoichiometry of this reaction is 1:2 NADH:Fe, supporting an overall scheme in which two Fe3+ ions are separately reduced by NADH in a stepwise fashion. We also observed that sulfur- and selenium-containing antioxidants alter cellular oxidative stress by changing the rate by which NADH reduces Fe3+ into hydroxyl radical-generating Fe2+. Fe3+ reduction rates with and without antioxidants were quantified, demonstrating that the sulfur and selenium compounds that prevent greater Fe2+-mediated DNA damage also enhance the rate of Fe3+ reduction by NADH. Antioxidant rescues in wild-type E. coli and a mutant strain (Δndh) with elevated (∼3 fold higher) NADH levels corroborated this counterintuitive trend: compounds that increased the Fe3+ reduction rate rescued more cells from H2O2-mediated killing. By uncovering this balance involving NADH and iron, we have identified a previously overlooked antioxidant mechanism for these Fe-binding antioxidants, one by which they interact with and modify NADH-Fe redox cycling.
{"title":"Sulfur and selenium compounds alter cellular oxidative stress by the NADH reduction of Fe3+ to Fe2+","authors":"Craig Goodman , Tyler Williams , Abigail G. McNamee , Julia L. Brumaghim","doi":"10.1016/j.ica.2025.123031","DOIUrl":"10.1016/j.ica.2025.123031","url":null,"abstract":"<div><div>Oxidative DNA damage in cells causes a variety of pathologies including but not limited to cancers, cardiovascular diseases, and neurodegenerative disorders. Fe<sup>3+</sup> reduction by NADH is the rate-limiting step in cellular hydroxyl radical generation and damage, but this aspect of the oxidative stress cycle is little explored. We established a rate law for the NADH-Fe system in vitro that indicates the Fe<sup>3+</sup> reduction rate depends primarily on NADH concentration, indicating that NADH may be a critical participant in cellular oxidative stress. Kinetic experiments using ferene established that the overall stoichiometry of this reaction is 1:2 NADH:Fe, supporting an overall scheme in which two Fe<sup>3+</sup> ions are separately reduced by NADH in a stepwise fashion. We also observed that sulfur- and selenium-containing antioxidants alter cellular oxidative stress by changing the rate by which NADH reduces Fe<sup>3+</sup> into hydroxyl radical-generating Fe<sup>2+</sup>. Fe<sup>3+</sup> reduction rates with and without antioxidants were quantified, demonstrating that the sulfur and selenium compounds that prevent greater Fe<sup>2+</sup>-mediated DNA damage also enhance the rate of Fe<sup>3+</sup> reduction by NADH. Antioxidant rescues in wild-type <em>E. coli</em> and a mutant strain (Δ<em>ndh</em>) with elevated (∼3 fold higher) NADH levels corroborated this counterintuitive trend: compounds that increased the Fe<sup>3+</sup> reduction rate rescued more cells from H<sub>2</sub>O<sub>2</sub>-mediated killing. By uncovering this balance involving NADH and iron, we have identified a previously overlooked antioxidant mechanism for these Fe-binding antioxidants, one by which they interact with and modify NADH-Fe redox cycling.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123031"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839360","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}