Inorganica Chimica Acta最新文献

{"title":"Structural and spectroscopic characterization of Zn(II) complexes: A computational perspective on anticorrosion potential of bronze surface","authors":"Amir Karim ,&nbsp;Munsif Jan ,&nbsp;Rahime Eshaghi Malekshah ,&nbsp;Najeeb Ullah ,&nbsp;Nida Ali ,&nbsp;Ali Haider ,&nbsp;Muhammad Iqbal ,&nbsp;Saqib Ali ,&nbsp;Sodio C.N. Hsu ,&nbsp;Muhammad Nawaz Tahir","doi":"10.1016/j.ica.2025.122731","DOIUrl":"10.1016/j.ica.2025.122731","url":null,"abstract":"<div><div>The coordination of Zn(II) carboxylates with nitrogen donor ligands significantly influences the physicochemical properties of metal complexes, due to their structural diversity. Herein, we report the synthesis and characterization of Zn(II) heteroleptic complexes with the general formulae [(<strong>L1</strong>)₂Zn(bipy)] (<strong>1</strong>), [(<strong>L2</strong>)₂Zn(bipy)] (<strong>2</strong>), [(<strong>L3</strong>)₂Zn(quinoline) (H₂O)] (<strong>3</strong>), [(<strong>L4</strong>)₂Zn(quinoline) (H₂O)] (<strong>4</strong>), and [(<strong>L5</strong>)₂Zn(quinoline) (H₂O)] (<strong>5</strong>), where <strong>L1</strong>–<strong>L5</strong> represent benzoic acid or phenyl acetic acid derivatives, and bipy denotes 2,2-bipyridne. All complexes were thoroughly characterized using FTIR, UV–vis, and ¹H/¹³C NMR (for complexes <strong>3</strong>–<strong>5</strong> only). The structures of <strong>1</strong> and <strong>2</strong> were further confirmed by single-crystal X-ray diffraction. All complexes are mononuclear, incorporating two carboxylate ligands. Complexes 1 and 2 contain one 2,2′-bipyridine ligand, while complexes <strong>3</strong>–<strong>5</strong> feature a quinoline ligand and a water molecule. Most of the complexes adopt hexacoordinated structures. However, complex <strong>1</strong> is tetra-coordinated, exhibiting a distorted tetrahedral geometry. Various coordination modes are observed, including both monodentate <strong>1</strong>, a combination of monodentate and bidentate (<strong>3</strong>–<strong>5</strong>), and both bidentate coordination <strong>2</strong>. All the complexes were optimized for their HOMO/LUMO energy by using DFT<img>D. The anticorrosion ability of all complexes was evaluated by Monte Carlo (MC) and molecular dynamics (MD) simulations. MC and MD simulations of complexes <strong>1</strong>–<strong>5</strong> on the bronze (100) surface, along with negative adsorption energies, reveal strong first-layer localization through both chemisorption and physisorption. The degree of adsorption of complexes <strong>1</strong>–<strong>5</strong> follows the order <strong>3</strong> &gt; <strong>2</strong> &gt; <strong>5</strong> &gt; <strong>4</strong> &gt; <strong>1</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122731"},"PeriodicalIF":2.7,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143892262","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}

{"title":"Trinuclear rhenium bromide cluster Re3Br9 as a product of thermal decomposition of Re3I3Br6 and a precursor for Re(CO)5Br","authors":"Elena Gorbachuk ,&nbsp;Maxim Mikhaylov ,&nbsp;Taisiya Sukhikh ,&nbsp;Maxim Sokolov ,&nbsp;Dmitry Yakhvarov","doi":"10.1016/j.ica.2025.122729","DOIUrl":"10.1016/j.ica.2025.122729","url":null,"abstract":"<div><div>The heating of Re₃I₃Br₆ up to 450 °C led to the formation of Re₃Br₉. Carbonylation of Re₃Br₉ with HCOOH at 130°С in concentrated HBr leads to the formation of Re(CO)₅Br in a good yield. The formation of Re₃Br₉ and Re(CO)₅Br was confirmed by single crystal X-ray diffraction analysis. The cluster phase Re₃Br₉ was characterized by powder X-ray diffraction analysis and energy-dispersive spectroscopy. Re(CO)₅Br was additionally identified by energy-dispersive spectroscopy and Raman spectroscopy. New structures have been determined for an aquation product of Re₃Br₉, [Re₃Br₉(H₂O)₃]·3Et₂O, and for (PyH)₂ReBr₆, which was obtained as pyridinium by extraction with HBr of a by-product of the thermal decomposition of Re₃I₃Br₆. Re₃I₃Br₆ was characterized by thermogravimetric analysis.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122729"},"PeriodicalIF":2.7,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143899115","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}

{"title":"A new non-centrosymmetric cuprate (II) hybrid compound [C16H36N]3(Cu2Br6)(CuBr3): Study of structural and dielectric behavior","authors":"Mouna Harzallah ,&nbsp;Yahya Bahrouni ,&nbsp;Ch. Rayssi ,&nbsp;Thierry Roisnel ,&nbsp;Abderrazek Oueslati ,&nbsp;Brahim Ayed","doi":"10.1016/j.ica.2025.122732","DOIUrl":"10.1016/j.ica.2025.122732","url":null,"abstract":"<div><div>A novel organic-inorganic hybrid material, [C₁₆H₃₆N]₃(Cu₂Br₆)(CuBr₃), was synthesized via slow evaporation and extensively characterized. Techniques such as X-ray diffraction, SEM/EDX, IR spectroscopy, and electric and dielectric studies were applied. Examination of the crystal structure reveals that the synthesized material adopts an orthorhombic system, specifically belonging to the <em>P</em>2₁2₁2 space group, with unit cell parameters a = 25.635 Å, b = 25.996 Å, c = 20.431 Å, V = 13615.3ų, and Z = 8. Purity confirmation was established through powder X-ray diffraction analysis. Composition verification was carried out using semiquantitative EDXS analysis. The asymmetric unit consists of three tetrabutylammonium organic cations [C₁₆H₃₆N]³⁺, two [Cu₂Br₆]²groups, and one [CuBr₃] group, forming a 0D anionic network. C–H⋯Br hydrogen bonding combines to create a 3D hydrogen-bonded network, maintaining crystal stability. IR spectral analysis corroborated the compound's characterstics at room temperature. Impedance spectroscopy highlighted the compound's electrical properties, and the fitting of the Nyquist plot revealed that both inter- and intra-grains contribute to relaxation. The equivalent circuit is modeled by a combination of two parallel R-CPEs connected in series to explain the impedance results.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122732"},"PeriodicalIF":2.7,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143892261","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}

{"title":"Synthesis, structure and luminescent sensing behaviour of a thieno[3,4-b]thiophene-based coordination polymer","authors":"Ye-Feng Wu,&nbsp;Yu-Chen Ma,&nbsp;Quan Yuan,&nbsp;Ze-Xu An,&nbsp;Yong-Jun Liu,&nbsp;Jun Yi,&nbsp;Xiao-Yan Tang,&nbsp;Yun-Sheng Ma,&nbsp;Wen-Yu Yin,&nbsp;Hong-Jian Cheng","doi":"10.1016/j.ica.2025.122733","DOIUrl":"10.1016/j.ica.2025.122733","url":null,"abstract":"<div><div>Thiophene-based functional materials have always been a research hotspot due to their broad application prospects in fields such as optoelectronics, sensing, biomedical science, etc. Solvothermal reaction of 3,6-di(pyridin-3-yl)-2,4-di(3-pyridylcarbonyl)thieno[3,4-<em>b</em>]thiophene (tptbt) with Cd(OAc)₂·2H₂O and 1,4-benzenedicarboxylic acid (1,4-H₂bdc) at 100 °C gave rise to one coordination polymer {[Cd(1,4-bdc)(tptbt]·0.75H₂O}_n (<strong>1</strong>). Complex <strong>1</strong> exhibits a 3D binodal (3,5)-connected network with the (4²·6)(4²·6⁵·8³) topology, which is formed by linking 1D [Cd(tptbt)]_n ribbon-like units with 1,4-bdc ligands. The solid state luminescences of tptbt and <strong>1</strong> were investigated. Complex <strong>1</strong> showed outstanding luminescent sensing performances for water, cations Fe³⁺ and anions Cr₂O₇²⁻ owing to the quenching effect. Moreover, the mechanochromic luminescences of tptbt and <strong>1</strong> were also tested.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122733"},"PeriodicalIF":2.7,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143883054","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}

{"title":"2-(1H-imidazol-2-yl)aniline bearing ligands and their cobalt complexes: Synthesis, characterisation, antimicrobial activity and oxidative coupling of o-aminophenol","authors":"Raymond Akong Akong ,&nbsp;Helmar Görls ,&nbsp;Joseph Anthony Orighomisan Woods ,&nbsp;Blessing Ifeoma Nwadike ,&nbsp;Abimbola Olumide Adekanmbi ,&nbsp;Winfried Plass ,&nbsp;Abiodun Omokehinde Eseola","doi":"10.1016/j.ica.2025.122716","DOIUrl":"10.1016/j.ica.2025.122716","url":null,"abstract":"<div><div>We report a family of imidazole based Schiff bases obtained by condensation of 2-(1<em>H</em>-imidazol-2-yl)aniline scaffolds with salicylaldehyde (<strong>HL</strong>_{<strong>1</strong>}, <strong>HL</strong>_{<strong>3</strong>} – <strong>HL</strong>_{<strong>5</strong>}) {<strong>HL</strong>_{<strong>1</strong>} = (<em>E</em>)-2-(((2-(4,5-diphenyl-1<em>H</em>-imidazol-2-yl)phenyl)imino)methyl)phenol; <strong>HL</strong>_{<strong>3</strong>} = (<em>E</em>)-2-(((2-(4,5-bis(4-methoxyphenyl)-1<em>H</em>-imidazol-2-yl)phenyl)imino)methyl)phenol; <strong>HL</strong>_{<strong>4</strong>} = (<em>E</em>)-2-(((2-(4,5-bis(4-methoxyphenyl)-1-methyl-1<em>H</em>-imidazol-2-yl)phenyl)imino)methyl)phenol; <strong>HL</strong>_{<strong>5</strong>} = (<em>E</em>)-2-(((2-(1,4,5-triphenyl-1<em>H</em>-imidazol-2-yl)phenyl)imino)methyl)phenol} and 2-pyridinecarboxaldehyde (<strong>L</strong>_{<strong>2</strong>} = (<em>E</em>)-2-(4,5-diphenyl-1<em>H</em>-imidazol-2-yl)-N-(pyridin-2-ylmethylene)aniline), as well as their homoleptic Co^II (<strong>1</strong>, <strong>2</strong>–<strong>7</strong>) {<strong>1</strong> = [CoL₁Cl]0.75H₂O.0.5MeOH; <strong>2</strong> = [CoL₁(OAc)]0.75H₂O; <strong>3</strong> = [CoL₂Cl₂]; <strong>4</strong> = [CoL₃Cl]1.5MeOH; <strong>5</strong> = [CoL₃(OAc)]; <strong>6</strong> = [CoL₄Cl]; <strong>7</strong> = [CoL₅Cl]} and Co^III (<strong>1v</strong> = [Co(L₁)₂]Cl.MeOH) complexes. The formulation of prepared compounds was determined by elemental analysis, NMR, MS, FT-IR, electronic absorption, magnetic susceptibility and single crystal X-ray analysis (<strong>1v</strong>, <strong>3</strong>, <strong>7</strong> and <strong>Co(I</strong>_{<strong>A4</strong>}<strong>)Cl</strong>_{<strong>2</strong>}). In the imine complexes, the Co<img>N bond lengths are longer in the neutral ligand (<strong>3</strong>) than in the anionic ligands (<strong>1v</strong> and <strong>7</strong>) and suggests high spin (HS) state in <strong>3</strong> and <strong>7</strong> (Co-<em>N</em> &gt; 2.0 Å) and low spin (LS) state in <strong>1v</strong> (Co-<em>N</em> &lt; 2.0 Å). The compounds were tested against Gram (+) and Gram (−) bacteria and exhibited better activity than one of the control used (especially in the case of <em>K. pne</em> and <em>C. freundii</em>). The catalytic efficiency of the complexes depends on the nature of the counter ion deployed, subtle changes in the molecular scaffolds and geometry.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122716"},"PeriodicalIF":2.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895212","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}

{"title":"A cadmium-based coordination polymer as multifunctional fluorescent sensor for simultaneous detection of heavy metal ions and antibiotics in water","authors":"Yun Cao ,&nbsp;Shuo Zhou ,&nbsp;Bei-Bei Yin ,&nbsp;Yan Wang","doi":"10.1016/j.ica.2025.122727","DOIUrl":"10.1016/j.ica.2025.122727","url":null,"abstract":"<div><div>This work successfully constructed a new three-dimensional coordination polymer [Zn(HEA)(L1)]_n (<strong>1</strong>) based on <em>o</em>-phenylenediacetic acid (H₂HEA) and 1,1′-(2,4,6-trimethyl-1,3-phenylene) bis(methylene) bis(1H-imidazole) (L1), demonstrating exceptional thermal stability and solvent resistance. The unique two-dimensional architecture of complex <strong>1</strong> features a distinctive “W”-shaped topology, assembled through the interconnection of nitrogen-rich and oxygen-containing coordination chains. These 2D layers subsequently extend into a three-dimensional framework via π–π stacking interactions and interlayer hydrogen bonding, creating a stable and porous network structure. As a multifunctional fluorescent probe, complex <strong>1</strong> exhibits remarkable sensing capabilities towards aqueous CrO₄²⁻, Cr₂O₇²⁻, and Fe³⁺ ions, and antibiotics including Ornidazole (ODZ) and Nitrofurazone (NFZ), with detection limits below 0.058 μM. Mechanistic investigations combining UV–vis absorption spectroscopy and density functional theory (DFT) calculations revealed that the fluorescence quenching originates from competitive energy absorption for metal ions, while a synergistic effect of photoinduced electron transfer (PET) and energy absorption accounts for antibiotic detection. Practical applicability was validated through real water sample analysis, achieving recovery rates of 97.3 %–103.7 % with relative standard deviations below 4 %. This study provides a new strategy for the simultaneous detection of multiple pollutants and expands the design principles for multifunctional fluorescent probes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122727"},"PeriodicalIF":2.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143874598","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}

{"title":"Biological activity evaluation and molecular docking studies of newly synthesized β-ketoiminato-based palladium complexes","authors":"Deeb Taher ,&nbsp;Naim.H. Al-Said ,&nbsp;Mohammad Albanna ,&nbsp;Matous Kloda ,&nbsp;Morad Mustafa ,&nbsp;Wissam Helal ,&nbsp;Khaleel I. Assaf ,&nbsp;Wafa Hourani ,&nbsp;Wael-Rémy Kotob ,&nbsp;Sundus Saleh ,&nbsp;Ahmad Makahleh ,&nbsp;Manar Mohammad Rabba'a","doi":"10.1016/j.ica.2025.122711","DOIUrl":"10.1016/j.ica.2025.122711","url":null,"abstract":"<div><div>A series of palladium(II) β-ketoiminato complexes, [Pd(CH₃C(<em>NAr</em>)CHC(O)Ph)₂] (<strong>4a</strong>–<strong>j</strong>), were synthesized <em>via</em> the reaction of N-aryl-substituted β-ketoiminate precursors with [PdCl₂(CH₃CN)₂] in the presence of ^<em>t</em>BuOK. Single-crystal X-ray diffraction of <strong>4a</strong>–<strong>h</strong> and <strong>4j</strong> confirmed a square-planar Pd(II) coordination. Notably, <strong>4b</strong> exhibited C–H···Pd anagostic interactions, contributing to lattice stability, which was further analyzed using Hirshfeld surface 2D fingerprint plots. Computational studies, including non-covalent interaction (NCI) plots and quantum theory of atoms in molecules (QTAIM), provided insights into these interactions. Complexes <strong>4a</strong>–<strong>j</strong> show characteristic ILCT (π → π *) bands in their UV–Vis spectra, which were additionally confirmed by TD-DFT calculations. DFT analysis reveals that the HOMO is composed of contributions from both the Pd(II) center and β-ketoiminato ligand orbitals, while the LUMO is primarily derived from β-ketoiminate ligand orbitals. The anticancer potential of <strong>4</strong>a–<strong>j</strong> was evaluated against MCF-7 and HT-29 cell lines. Complexes <strong>4a</strong>–<strong>d</strong> and <strong>4f</strong> exhibited significant cytotoxicity, effectively inhibiting HT-29 cell migration. Among them, <strong>4c</strong> demonstrated the highest potency, with an IC50 of 1.73 μM, significantly reducing HT-29 cell viability. The ability of Pd(II) complexes to interact with three targeted proteins, namely, PIK3CA-E545K, ERBB4-Y1242C, and BRAF-V600E was evaluated through molecular docking studies, revealing moderate to high binding affinities. Notably, complex <strong>4c</strong> demonstrated the strongest interactions across all targets.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"583 ","pages":"Article 122711"},"PeriodicalIF":2.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863628","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}

{"title":"Dinitrogen fixation by alkali and alkaline earth hydride composites under plasma","authors":"Kai Ma ,&nbsp;Jianping Guo ,&nbsp;Ping Chen","doi":"10.1016/j.ica.2025.122720","DOIUrl":"10.1016/j.ica.2025.122720","url":null,"abstract":"<div><div>The development of alternative methods for sustainable dinitrogen (N₂) fixation to ammonia (NH₃) is a cutting-edge research area. The presence of external stimuli, such as non-thermal plasma, can boost the activation of the inert N₂ molecules under ambient temperatures and pressures, thereby generating value-added products such as NH₃ or other nitrogen-containing compounds. Binary alkali metal hydrides such as NaH and KH have recently shown intriguing properties in the plasma nitrogen fixation process. Herein we report the different chemical behaviors of a series of hydride composites consist of potassium hydride (KH) and alkaline earth metal hydride (MgH₂, CaH₂, SrH₂, and BaH₂) under nitrogen plasma conditions. A nitrogen-relayed mechanism has been proposed to understand the different nitrogen fixation behaviors on these hydride composites. Under this scenario, KH is responsible for plasma N₂ fixation to form surface NH₂ species, which subsequently migrate and react with MgH₂, CaH₂, and SrH₂ to form N and NH species, respectively. This work enriches the plasma chemistry of metal hydrides, and provides a strategy to enhance the amounts of fixed nitrogen of single hydride material under nitrogen plasma conditions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122720"},"PeriodicalIF":2.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143874597","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}

{"title":"An overview of the synthesis, structure, property and application of copper(II) and nickel(II) complexes of salicylaldehyde semicarbazone derivatives","authors":"Puspendu Middya,&nbsp;Subhayubrata Ganguly,&nbsp;Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.122722","DOIUrl":"10.1016/j.ica.2025.122722","url":null,"abstract":"<div><div>Different semicarbazone Schiff base ligands, prepared by the condensation of a semicarbazide and a salicylaldehyde derivative, have been used in the synthesis of varieties of mono-, di-, tri, tetra- and poly-nuclear complexes with several transition and non-transition metals. This review focuses on the synthesis of nickel(II) and copper(II) complexes with these semicarbazone Schiff base ligands. The X-ray structures, different biological activity and magnetic property of these complexes are also discussed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122722"},"PeriodicalIF":2.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143894388","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}

{"title":"Dinuclear Cu(II) and Ni(II) complexes with bis(pyridylimine) ligands: Comparative analysis of the reactivity of ligated imine and an in-depth investigation of the DNA/complex interactions","authors":"Daniel L. Singer ,&nbsp;Isabella R. Demyan ,&nbsp;Emily Stein ,&nbsp;Abigail R. Bowman ,&nbsp;Paige E. Tromblee ,&nbsp;Jason G. Marmorstein ,&nbsp;Kennedy A. Alexis ,&nbsp;Joseph M. Tanski ,&nbsp;Timothy J. Barnum ,&nbsp;Colleen M. Connelly ,&nbsp;Laurie A. Tyler","doi":"10.1016/j.ica.2025.122721","DOIUrl":"10.1016/j.ica.2025.122721","url":null,"abstract":"<div><div>The reactions of hydrated Cu(ClO₄)₂ and NiCl₂ with substituted bis(pyridylimine) ligands ((PyR)₂en, where R = Me or OMe on the 6-position of the pyridine) have been carried out and the product characterization for four new dinuclear complexes are reported, including single crystal XRD as well as UV/Vis and IR spectroscopic analyses supported by DFT calculations. The copper(II) complexes of both ligands resulted in the formation of analogous species, namely [(Cu((PyMe)enH₂))₂(PyMe)₂en](ClO₄)₄ (<strong>1</strong>) and [(Cu((PyOMe)enH₂))₂(PyOMe)₂en](ClO₄)₄ (<strong>2</strong>), which contain a full ligand bridging the two metal centers and a tridentate, non-bridging partially hydrolyzed ligand (PyR)enH₂. In contrast, the reaction with hydrated Ni(II) chloride resulted in [Ni((PyMe)₂en)Cl]₂Cl₂ (<strong>3</strong>) and [Ni(PyOMe₂(en))Cl]₂[NiCl₄] (<strong>4</strong>), which do not contain hydrolyzed ligand in the coordination sphere. The effect of the metal center and the starting salt in promoting ligand hydrolysis is discussed. The biological activity including in vitro DNA binding and cleavage was also evaluated for complexes <strong>1</strong>–<strong>4</strong>. Ethidium bromide displacement assays with calf thymus DNA showed concentration-dependent displacement and DNA binding for all complexes, with apparent binding constants between 4 and 6.5 × 10⁵ M⁻¹. Cu(II) complexes <strong>1</strong> and <strong>2</strong> were further able to cleave DNA in vitro, producing both single-nicked and double-nicked DNA, while the Ni(II) complexes <strong>3</strong> and <strong>4</strong> showed no DNA cleavage under the same conditions. Investigations into the cleavage by the Cu(II) complexes <strong>1</strong> and <strong>2</strong> revealed an oxidative mechanism, where the complexes utilize O₂⁻ and ¹O₂ as the primary radical oxygen species, with ·OH playing a lesser role in the activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"584 ","pages":"Article 122721"},"PeriodicalIF":2.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885922","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}