Inorganica Chimica Acta最新文献

{"title":"Correlation between thermal conductivity of nanofluids and their structural, electronic and thermodynamic properties: DFT study","authors":"Hicham Salhi ,&nbsp;Nadjib Chafai ,&nbsp;Khalissa Benbouguerra ,&nbsp;Krishna Kumar Yadav ,&nbsp;Mohammad Khalid ,&nbsp;Ghadah Shukri Albakri","doi":"10.1016/j.ica.2025.122919","DOIUrl":"10.1016/j.ica.2025.122919","url":null,"abstract":"<div><div>In this study, we address the critical challenge of enhancing thermal conductivity in nanofluids, a key factor for improving heat transfer efficiency in various industrial applications. Using density functional theory (DFT), we systematically investigate the relationship between thermal conductivity and the structural, electronic, and thermodynamic properties of Silver (Ag), Copper (Cu), Gold (Au), and Aluminum (Al) nanofluids. We analyze quantum chemical parameters, including molecular orbital energies, energy gap (Δ<em>E</em>_GAP), ionization potential (<em>I</em>), electron affinity (<em>A</em>), hardness (<em>η</em>), and local softness (<em>σ</em>), alongside thermodynamic properties such as enthalpy (Δ<em>H</em>), Gibbs free energy (Δ<em>G</em>), entropy (Δ<em>S</em>), and heat capacity (<em>C</em>v). Our results demonstrate that Ag nanofluids exhibit superior thermal conductivity (429 W/m·K), supported by their high values of <em>E</em>_HOMO (−3.5325 eV), <em>E</em>_LUMO (−2.0781 eV), and <em>σ</em> (1.3751), as well as low values of Δ<em>E</em>_GAP (1.4544 eV), <em>I</em> (3.5325 eV), <em>A</em> (2.0781 eV), and <em>η</em> (0.7272 eV). These findings reveal a strong correlation between thermal conductivity and quantum chemical parameters. Additionally, thermodynamic calculations for Ag and Al nanofluids highlight that the high thermal conductivity of Ag is driven by its elevated Δ<em>H</em>, Δ<em>S</em>, and <em>C</em>v values. This work provides novel insights into the design of high-performance nanofluids by establishing a quantitative link between thermal conductivity and fundamental material properties, advancing beyond previous studies in the literature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122919"},"PeriodicalIF":3.2,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106879","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 3D arsenomolybdate-based organic-inorganic hybrid with the electrochemical sensing of ascorbic acid","authors":"Qiao Gao ,&nbsp;Miao Miao ,&nbsp;Xue-Rui Dong ,&nbsp;Lin Xu","doi":"10.1016/j.ica.2025.122920","DOIUrl":"10.1016/j.ica.2025.122920","url":null,"abstract":"<div><div>The design and preparation of efficient polyoxometalate-based electrocatalytic materials present a viable approach to achieve sensitive electrochemical sensing of ascorbic acid (AA). Herein, we report the synthesis of a novel organic-inorganic hybrid compound, H(H₂en)₃[AsMo₈V₄O₄₀]·11H₂O (<strong>1</strong>) (en = ethylenediamine), via a facile one-pot self-assembly method. Single-crystal X-ray diffraction analyses show that hybrid <strong>1</strong> features a three-dimensional (3D) supramolecular architecture, where arsenomolybdate [AsMo₈V₄O₄₀]⁷⁻ clusters are interconnected through hydrogen bonding interactions with protonated [H₂en]²⁺ cations. Electrochemical analyses verified the excellent electrocatalytic activity of hybrid <strong>1</strong> toward AA oxidation. When utilizing hybrid <strong>1</strong> as an electrode material, the developed electrode exhibited superior analytical performance for detecting AA. It featured a wide linear detection range from 30 to 270 μM, a high sensitivity of 0.044 μA·μM⁻¹, a low detection limit of 6.78 μM, and favorable selectivity and stability.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122920"},"PeriodicalIF":3.2,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106882","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":"Influence of synthesis methods on the crystal structure and third-order nonlinear optical properties of calcium-based coordination polymers","authors":"M.R. Sabitha Mohan ,&nbsp;I. Hubert Joe ,&nbsp;P. Aswathy","doi":"10.1016/j.ica.2025.122903","DOIUrl":"10.1016/j.ica.2025.122903","url":null,"abstract":"<div><div>This work investigates how different synthesis methods affect the crystal structure and third-order nonlinear optical (NLO) properties of coordination polymers formed from calcium chloride dihydrate and salicylic acid. Single crystals of the compounds were prepared using silica gel diffusion (CalSal) and slow evaporation (CalSalD) methods. In both cases, high-quality crystals were obtained at an optimal concentration of 0.5 M for both the metal salt and the ligand solutions. Single-crystal X-ray diffraction revealed that CalSalD possesses a novel crystal structure, while CalSal exhibits a previously known structure. However, this is the first report of CalSal being synthesised in a gel medium. The compounds were further characterised using FTIR spectroscopy, thermal analysis, and UV–visible spectroscopy. Third-order NLO studies using the <em>Z</em>-scan technique demonstrated distinct nonlinear optical properties for the two compounds, underscoring their potential in photonic and optoelectronic applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122903"},"PeriodicalIF":3.2,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061241","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 of rare earth nitrate complexes with 4′-pyridin-4-yl-terpyridine and their solid-state transformation to coordination polymers","authors":"Alexander Sedykh ,&nbsp;Dirk G. Kurth ,&nbsp;Klaus Müller-Buschbaum","doi":"10.1016/j.ica.2025.122911","DOIUrl":"10.1016/j.ica.2025.122911","url":null,"abstract":"<div><div>The interaction of the series of trivalent rare earth (RE) nitrates with 4′-(pyridin-4-yl)-2,2′:6′,2″-terpyridine (<strong>4-pytpy</strong>) was investigated. In direct reaction between RE(NO₃)₃·nH<em>2</em>O with <strong>4-pytpy</strong>, both, a series of isotypic complexes [RE(NO₃)₃(4-pytpy)(H₂O)] (<strong>1a-RE</strong> with CN 10 and <strong>1b-RE</strong> with CN 9) and the structurally individual complexes [La(NO₃)₃(4-pytpy)(H₂O)₂] (<strong>2</strong>) and [Sc(NO₃)₂(4-pytpy)(H₂O)]NO₃ (<strong>3</strong>) were obtained. The thermal stability of the phases was investigated using simultaneous differential thermal analysis and thermogravimetry (DTA/TG or STA) as well as high-temperature powder X-ray diffraction analysis (HT-PXRD). Coordinated water can be removed from complexes <strong>1</strong>–<strong>3</strong>, resulting in the formation of coordination polymers ¹_∞[RE(NO₃)₃(4-pytpy)] (<strong>4-RE</strong>) for early and middle lanthanides as well as [RE(NO₃)₃(4-pytpy)] (<strong>5-RE</strong>) for late lanthanides, yttrium, and scandium. At elevated temperatures (150–370 °C), the polymeric structure <strong>4-RE</strong> with a connection via organic linker dissociates, and a series of dimers [RE₂(NO₃)₆(4-pytpy)₂] (<strong>6-RE</strong>) bridged via nitrates are formed; the temperature of this transition reduces along the lanthanide series. In general, the accessibility of the phases and solid-state transformations depends on the ionic radius of the trivalent rare earth element. Photophysical properties of Eu³⁺ and Tb³⁺ were determined in the solid state. The absolute photoluminescence quantum yield (PLQY) of polymorphs presented here depends on the packing, which determines the ligand energy levels. Highlight is ¹_∞[Eu(NO₃)₃(4-pytpy)] (<strong>4-Eu</strong>) with the PLQY of 79.3(9) %. In addition to single-crystal X-ray diffraction (SCXRD), 3D electron diffraction analysis (3D-ED) was used for the determination of crystal structures.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122911"},"PeriodicalIF":3.2,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118910","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 palladium(II) complex containing ethylenediamine and 2-thioxo-4-thiazolidinone exhibits high activity against resistant Campylobacter jejuni strains","authors":"Meiry Leandra de Lacerda ,&nbsp;Letícia Roberta Martins Costa ,&nbsp;Dayanne Maria da Silva Coimbra ,&nbsp;Gabriele de Menezes Pereira ,&nbsp;Clara Maria Faria Silva ,&nbsp;Pedro Paulo Corbi ,&nbsp;Daise Aparecida Rossi ,&nbsp;Robson José de Oliveira Júnior ,&nbsp;Roberta Torres de Melo ,&nbsp;Wendell Guerra","doi":"10.1016/j.ica.2025.122913","DOIUrl":"10.1016/j.ica.2025.122913","url":null,"abstract":"<div><div>This manuscript describes the synthesis and spectroscopic characterization of two new Pt²⁺ and Pd²⁺ complexes containing ethylenediamine (en) and 2-thioxo-4-thiazolidinone (L1) as ligands. Infrared and NMR data suggest that L1 coordinates to the metal ions in a monodentate manner by the sulfur atom (S⁻). The coordination sphere of the metals is completed by an ethylenediamine molecule coordinated by the two nitrogen atoms. The metal complexes were evaluated against six resistant strains of <em>Campylobacter jejuni.</em> The Pd²⁺ complex (<strong>1</strong>) was more active than the Pt²⁺ complex (<strong>2</strong>) and the free ligand (L1), exhibiting high to moderate activity (MBC between 1.56 and 100 μg/mL) against the strains tested. Thereafter, the Pd²⁺ complex was evaluated in a tumoral cell line (B16-F10, murine melanoma) and in two non-tumoral cell lines (NIH/3 T3, mouse fibroblast, and C2C12, mouse myoblast), but no significant activity was observed (IC₅₀ values ≥137.3 μM), suggesting that it does not exhibit considerable toxicity. Thus, the biological data reported here indicate that the Pd²⁺ complex is a promising antibacterial agent which deserves further investigation, since there is a strong need to produce new drugs that are active against multidrug-resistant pathogens.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122913"},"PeriodicalIF":3.2,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047251","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":"Silane-modified lanthanide complexes for integration into hybrid coatings and nanoparticles: thermal sensing applications and live cell labeling","authors":"Ivan Sedmak ,&nbsp;Aljoša Bolje ,&nbsp;Jakob Kljun ,&nbsp;Rok Podlipec ,&nbsp;Hana Kokot ,&nbsp;Sebastjan Nemec ,&nbsp;Slavko Kralj ,&nbsp;Peter Rodič ,&nbsp;Iztok Golobič ,&nbsp;Stane Pajk","doi":"10.1016/j.ica.2025.122904","DOIUrl":"10.1016/j.ica.2025.122904","url":null,"abstract":"<div><div>Temperature sensing at the micro- and nanoscale remains a significant challenge due to the limitations of conventional techniques in spatial resolution and invasiveness. Here, we report the development of luminescent, temperature-sensitive coatings and nanoparticles based on a newly synthesized europium (Eu) complex integrated into a composite poly(methyl methacrylate)-siloxane-silica (PMMA-siloxane silica) matrix. The Eu complex, identified as the most promising candidate among three lanthanide complexes, was functionalized with silyl ethers via copper-catalyzed azide-alkyne cycloaddition and successfully incorporated into thin PMMA-siloxane silica films on glass surfaces and within silica nanoparticles. These materials exhibited strong thermal responsiveness, chemical stability, and suitability for high-resolution temperature sensing. Furthermore, Eu-loaded silica nanoparticles showed a distinct fluorescent signal and multiplexing capability in live-cell confocal microscopy and were internalized by lung epithelial cells (LA-4 cell line), highlighting their potential as bioimaging probes for localized intracellular temperature sensing. Although some photobleaching was observed under prolonged excitation, the materials demonstrated sufficient chemical and mechanical stability, making them promising for luminescent temperature sensing and live-cell imaging. These results establish the developed Eu-based hybrid materials as robust, non-invasive luminescent probes for high-resolution thermal sensing and cellular imaging.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122904"},"PeriodicalIF":3.2,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047249","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 and characterization of novel Rh-NHC complexes: addition of phenylboronic acid to aldehydes, DFT/TD-DFT, and QTAIM studies","authors":"Öznur Doğan Ulu ,&nbsp;Sümeyya Serin ,&nbsp;İsmail Özdemir","doi":"10.1016/j.ica.2025.122909","DOIUrl":"10.1016/j.ica.2025.122909","url":null,"abstract":"<div><div>Herein, three new Rh(I)-NHC complexes (<strong>2a-c</strong>) were synthesized by reacting benzimidazolium salts with the [Rh(OMe)(COD)]₂ compound. The structures of the synthesized compounds were elucidated by various spectroscopic methods such as ¹H, ¹³C NMR, FT-IR, and UV–vis spectroscopies, and the elemental analysis technique. A thorough theoretical investigation was conducted to explore the electronic structure, reactivity, donor-acceptor interactions, and thermodynamic properties of newly synthesized Rh-NHC complexes. To this end, Density Functional Theory (DFT) calculations were utilized. The findings reveal that the 3,4,5-trimethoxybenzyl substitution contributes to the formation of a more stable and rigid structure in the Rh complex. Additionally, TD-DFT calculations were performed to assess the potential electronic transitions of the complexes <strong>2a-c</strong> within a chloroform environment. It is possible to interpret the observed peaks of the three complexes as predominantly associated with intra-ligand π → π* transitions and metal-ligand charge-transfer (MLCT) transitions. The quantum theory of atoms in molecules (QTAIM) was employed to facilitate comprehension of bond characteristics and intermolecular interaction strengths in <strong>2a-c</strong> complexes. Furthermore, the complexes were evaluated in the reaction of phenylboronic acid to aldehydes, and satisfactory yields were obtained for the desired products.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122909"},"PeriodicalIF":3.2,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046891","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 novel CuI coordination polymer featuring a trimethylenediamine Schiff base ligand: Structural, spectroscopic, theoretical, and molecular docking studies","authors":"Hadi Kargar ,&nbsp;Mehdi Fallah-Mehrjardi ,&nbsp;Fatemeh Abyar ,&nbsp;Necmi Dege ,&nbsp;Ersin Acar ,&nbsp;Muhammad Ashfaq ,&nbsp;Khurram Shahzad Munawar ,&nbsp;Muhammad Nawaz Tahir","doi":"10.1016/j.ica.2025.122910","DOIUrl":"10.1016/j.ica.2025.122910","url":null,"abstract":"<div><div>In this work, we synthesized a new polymeric Cu(I) complex, <strong>[Cu(L</strong>^{<strong>4Br</strong>}<strong>)I]</strong>_{<strong>n</strong>}, derived from a Salpn-type Schiff base ligand (<strong>L</strong>^{<strong>4Br</strong>} = <em>N,N′</em>-bis(4-bromobenzylidene)propane-1,3-diamine). In addition to NMR studies, the crystal structure was determined using single-crystal X-ray diffraction (SC-XRD), revealing that the Schiff base copper complex forms a binuclear one-dimensional (1D) polymer. In this structure, copper and iodide atoms form polymeric linkages, while both imine nitrogen atoms of the Schiff base coordinate with the copper centers. The Schiff base and iodide ligands coordinate to the copper centers, resulting in a slightly distorted trigonal planar geometry around each Cu atom. Hirshfeld surface analysis revealed that H┄I interactions are the dominant contributors to the supramolecular architecture, while the Cu<img>I pairs exhibit the highest interaction tendency, corresponding to the formation of polymeric bonds. The unit cell contains 11.1 % void space, indicating a minimal volume that suggests favorable mechanical properties. The molecular structure was optimized using the B3LYP functional with the Def2-TZVP basis set, showing good agreement between the calculated and experimental I<img>Cu and Cu<img>N bond lengths. Molecular electrostatic potential (MEP) analysis revealed electron-rich regions around electronegative atoms, particularly iodine and nitrogen, as potential sites for interactions with electrophilic species. NBO analysis indicated significant electron donation from halides to adjacent copper centers, highlighting their strong donor capability within the coordination sphere. The copper atoms exhibit positive NPA charges (∼0.35), confirming their electron-accepting role as metal centers. The optimized geometry of the complex <strong>[Cu(L</strong>^{<strong>4Br</strong>}<strong>)I]</strong>_{<strong>n</strong>} was used as input for molecular docking studies performed with AutoDock Vina. Binding constants (K_b) for DNA and BSA were calculated using the equation ΔG°_b = −RTlnK_b, where the calculated negative ΔG°_b values confirm the spontaneity of the binding processes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122910"},"PeriodicalIF":3.2,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046896","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 synthetic method of [Ru(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)Cl]+ complexes using cis-[Ru(2,2′:6′,2″-terpyridine)(NCCH3)2Cl]+ as an intermediate and comparison to a method using [Ru(benzene)(2,2′-bipyridine)Cl]+ intermediates","authors":"Stephen J. Tereniak,&nbsp;Benjamin J. Butler","doi":"10.1016/j.ica.2025.122892","DOIUrl":"10.1016/j.ica.2025.122892","url":null,"abstract":"<div><div>A new method of synthesizing [Ru(terpy)(bpy)Cl]⁺ (terpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine) complexes using the starting material <em>cis</em>-[Ru(terpy)(NCCH₃)₂Cl](PF₆) is reported. The yields of four derivatives ([Ru(terpy)(NN)Cl](PF₆): NN = bpy, <strong>1</strong>; 4,4′-(MeO)₂bpy, <strong>2</strong>; 4,4′-(CF₃)₂bpy, <strong>3</strong>; 2,2′-biquinoline, <strong>4</strong>) with this method range from 58 to 94 % and are similar to or greater than a known reaction in which the starting material is [Ru(benzene)(NN)Cl](PF₆). However, the use of <em>cis</em>-[Ru(terpy)(NCCH₃)₂Cl](PF₆) results in lower levels of homoleptic Ru byproducts in the synthesis of <strong>1</strong> as compared to the use of [Ru(benzene)(bpy)Cl](PF₆) as determined by ¹H NMR spectroscopy. Additionally, a high-purity and gram-scale synthesis of <em>cis</em>-[Ru(terpy)(NCCH₃)₂Cl](PF₆) that does not use column chromatography is reported, in contrast to the original synthesis disclosed in the literature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122892"},"PeriodicalIF":3.2,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106878","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":"Supramolecular assemblies in mononuclear Zn(II) and dinuclear Co(II) coordination compounds involving pyridines and methyl benzoates: Antiproliferative evaluation and theoretical studies","authors":"Subham Banik ,&nbsp;Kamal K. Dutta ,&nbsp;Rosa M. Gomila ,&nbsp;Antonio Frontera ,&nbsp;Miquel Barcelo-Oliver ,&nbsp;Akalesh K. Verma ,&nbsp;Diksha Dutta ,&nbsp;Manjit K. Bhattacharyya","doi":"10.1016/j.ica.2025.122902","DOIUrl":"10.1016/j.ica.2025.122902","url":null,"abstract":"<div><div>Two new metal-organic coordination compounds of Zn(II) and Co(II) viz. [Zn(3-CNpy)₂(H₂O)₄](4-Mebz)₂ (<strong>1</strong>)and [Co₂(<em>μ</em>-H₂O)(py)₄(<em>μ</em>-2-Mebz)₂(2-Mebz)₂] (<strong>2</strong>) (3-CNpy = 3-cyanopyridine, 4-Mebz = 4-methylbenzoate, 2-Mebz = 2-methylbenzoate, py = pyridine) have been synthesized and characterized using single crystal X-ray study, elemental analysis, FT-IR, electronic spectroscopy and thermogravimetric analysis (TGA). Compound <strong>1</strong> crystallizes as a mononuclear Zn(II) complex, whereas compound <strong>2</strong> is a water and <em>2-Mebz</em> bridged dinuclear coordination compound of Co(II). Crystal structure analysis of compound <strong>1</strong> highlights the presence of aromatic π stacking, π–π(CN) and O⋯O dichalcogen bonding interactions along with interesting charge-assisted hydrogen bonding interactions which together stabilize the layered assembly of the compound. Again, antiparallel π-stacking combined with C<img>H⋯π and C<img>H⋯O hydrogen bonding interactions stabilize the crystal packing of compound <strong>2</strong>. To characterize and rationalize these interactions, we utilized various computational tools, including DFT, MEP surface calculations, QTAIM analysis and NCIplot. Theoretical studies confirm the existence of structure-directing π–π(CN), π-stacking and H-bonding interactions involving strong O<img>H⋯O contacts (−42.4 kcal/mol) in <strong>1</strong>. Significantly negative dimerization energies (−29.0 kcal/mol) were obtained for <strong>2</strong>. The in vitro antiproliferative effects of compounds <strong>1</strong> and <strong>2</strong> were assessed on Dalton's lymphoma (DL) malignant cancer cell lines and normal PBMC cells using MTT, Trypan blue and eosin staining assays, demonstrating higher cytoxicity of compound <strong>2</strong> than compound <strong>1</strong>. The IC₅₀ values (DL) obtained for compounds <strong>1</strong> and <strong>2</strong> were 62.7<em>μ</em>Μ and 22.7<em>μ</em>Μ respectively. Molecular Docking studies of the compounds with antiapoptotic proteins showed that compound <strong>2</strong> interacted more effectively [binding score: −93.18 kcal/mol⁻¹ (MCL-1)] than compound <strong>1</strong> [binding score: 67.61 kal/mol⁻¹ (MCL-1)].</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122902"},"PeriodicalIF":3.2,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020498","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}