Inorganica Chimica Acta最新文献

{"title":"Electroreforming of methanol employing in-house prepared PtRu/C anode catalysts for hydrogen generation at the cathode","authors":"Carmelo Lo Vecchio,&nbsp;Angelo Mondello,&nbsp;Riccardo Dollenz,&nbsp;Erminia Mosca,&nbsp;Vincenzo Baglio","doi":"10.1016/j.ica.2025.123028","DOIUrl":"10.1016/j.ica.2025.123028","url":null,"abstract":"<div><div>The increasing global energy demand and the environmental impacts of fossil fuel consumption have driven the exploration of sustainable energy alternatives. Hydrogen is a promising clean energy carrier, particularly when produced via renewable-powered electrolysis. However, the efficiency of conventional water electrolysis is limited by the sluggish kinetics of the oxygen evolution reaction (OER). This study explores methanol electrooxidation as a more energy-efficient anodic alternative to OER in hydrogen generation systems. We synthesized 50 wt% Pt₁Ru₁ catalysts supported on Ketjenblack carbon (PtRu/C) via two sulphite-complex-based routes: (i) sequential impregnation of Ru onto preformed Pt-sulphite complexes, and (ii) direct mixing of Pt- and Ru-sulphite precursors. The resulting catalysts were characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) to assess their crystallinity, phase composition, morphology, and surface properties. The electrochemical performance was evaluated through methanol electroreforming experiments conducted in a membrane–electrode assembly (MEA) configuration. Full-cell tests conducted at 90 °C revealed an initial enhancement in performance for the catalyst with Ru impregnated onto Pt-sulphite, despite the presence of some non-alloyed Ru particles. In contrast, the PtRu/C-based MEA prepared by mixing Pt- and Ru-sulphite exhibited superior durability during a 24-h chronopotentiometric test, likely due to Pt<img>Ru alloy formation and the enhanced stability of Ru within the alloy. These results confirm the potential of optimized PtRu/C systems for efficient hydrogen production via methanol electroreforming and highlight the importance of synthesis strategy in tuning electrocatalyst performance and durability.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123028"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734156","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":"Investigation of vibrational properties of rare-earth ruddlesden-popper nickelates Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd)","authors":"Neenu Saini ,&nbsp;Ruby Jindal ,&nbsp;Archana Tripathi ,&nbsp;Uma Shekhawat ,&nbsp;Reechu Saini ,&nbsp;Naveen Kumar","doi":"10.1016/j.ica.2025.123005","DOIUrl":"10.1016/j.ica.2025.123005","url":null,"abstract":"<div><div>The Raman and Infrared (IR) phonon analysis of monolayer Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper (RP) Nickelates in the tetragonal phase, which have potential applications as electrocatalysts for solid oxide cells, has been carried out using normal coordinates. The Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper compounds possess <span><math><msubsup><mi>D</mi><mn>17</mn><mrow><mn>4</mn><mi>h</mi></mrow></msubsup></math></span> Point Group Symmetry, fall under the space group 139, and crystallize in the phase I4/mmm with a formula unit number Z = 2. The Layered Perovskite Oxides Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) represent the initial members of the Ruddlesden-Popper Nickelates Series, which are structurally defined by the general stoichiometry Ln_n+1Ni_nO_3n+1 (Ln = La, Pr, Nd, Eu, Gd) with <em>n</em> = 1. The theoretical analysis of the optical phonon modes in Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates crystallizing in the I4/mmm structural phase employs a set of nine Short-Range Force Constants (SRFCs). Wilson's GF-Matrix Method has characterized and assigned the optical vibrational modes in rare-earth Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) Ruddlesden-Popper Nickelates. The study further investigates the impact of the A-site Lanthanide cation-Ln (Ln = La, Pr, Nd, Eu, Gd) substitution on the lattice dynamics of the isostructural compounds Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) within the framework of monolayered tetragonal structures. To elucidate the effects of cation-Ln substitution, a comparative analysis of the frequencies at the zone centre, bond lengths, and force constants is conducted. The vibrational frequencies primarily governed by the Ln-atoms (Ln = La, Pr, Nd, Eu, Gd) display unique features that change with atomic number, highlighting the significant influence of Ln-ion size on the phonon dynamics of Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) rare-earth Nickel Oxides. Furthermore, for each normal mode in the Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) rare-earth Ruddlesden-Popper Nickelates, the study of Potential Energy Distribution (PED) emphasizes the considerable role played by Short-Range Force Constants in shaping the wavenumbers, thereby offering a deeper insight into the lattice dynamics and interatomic interactions. Layered Perovskite Oxides Ln₂NiO₄ (Ln = La, Pr, Nd, Eu, Gd) exhibit key Ln<img>O and Ni<img>O phonon modes that govern oxygen ion transport, defect chemistry, and SOFC efficiency.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123005"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645729","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":"Factors influencing imine activation in M(II) complexes to afford ligated N,O-aminal and hemiacetal groups: XRD, 1H NMR, and computational studies","authors":"Daniel L. Singer ,&nbsp;Jason G. Marmorstein ,&nbsp;Joseph M. Tanski ,&nbsp;Timothy J. Barnum ,&nbsp;Laurie A. Tyler","doi":"10.1016/j.ica.2025.123007","DOIUrl":"10.1016/j.ica.2025.123007","url":null,"abstract":"<div><div>The reactivity of ligated imines with alcohol-type nucleophiles has been investigated. Four Cu (II) complexes containing a <em>N,N′</em>-bis (2-pyridinylmethylene)-1,2-ethanediamine ((Py)₂en) type ligand are reported, along with the hydrolysis or addition of solvent methanol across the imine C<img>N bond. The products of this reactivity include the formation of ligated <em>N,O</em>-aminal or hemiacetal moieties as confirmed through single crystal X-ray crystallography. The observed product distribution is supported with ab initio and density functional theory calculations. A comprehensive ¹H NMR study was performed with further derivatized ligand frames and diamagnetic Zn (II) species to explore the scope of the observed reactivity. These studies indicate that the ligand substituent strongly impacts the degree of imine activation toward reaction with solvent methanol and/or water (i.e. formation of mono <em>N,O</em>-aminal, bis <em>N,O</em>-aminal, hemiacetal or no reaction). The identity of the counterion in the hydrated zinc salt was also found to play a role, albeit to a lesser extent. The implications of the identity of the alcohol solvent on the C<img>N reactivity was also investigated. Alcohols with decreased steric hindrance and increased nucleophilicity show the greatest propensity for addition.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123007"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734154","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 water-soluble Schiff base ligand and its Al(III) complex: optical properties, computational studies and photocatalytic performance","authors":"Hajer Bouznif ,&nbsp;Licínia L.G. Justino ,&nbsp;Telma Costa ,&nbsp;Maria I.L. Soares ,&nbsp;M. Luísa Ramos ,&nbsp;Teresa M.V.D. Pinho e Melo ,&nbsp;Nabil Zouari ,&nbsp;Rui Fausto","doi":"10.1016/j.ica.2025.123014","DOIUrl":"10.1016/j.ica.2025.123014","url":null,"abstract":"<div><div>Although the field of inorganic photophysics and photochemistry has traditionally been dominated by complexes of precious and rare metals, increasing concerns regarding their scarcity and cost have led to a growing interest in earth-abundant metal-based compounds as more sustainable and economically viable alternatives. In this study, we investigated the photophysical properties of two water-soluble compounds: the di-Schiff base <em>N</em>,<em>N′</em>-bis(3-methoxy-5-sulfonatosalicylidene)-1,2-ethylenediamine disodium salt (<strong>MSS</strong>) and its corresponding Al(III) complex. To better understand the enol-imine (O-H···N) <em>vs.</em> keto-enamine (O···H-N) tautomeric behavior of <strong>MSS</strong>, we also considered its non-methoxy analogue (<strong>SS</strong>) as a reference compound. Using UV–vis absorption and diffuse reflectance spectroscopy, we examined the tautomeric preferences of <strong>MSS</strong> and <strong>SS</strong> in both the solid state and various solvents. The spectral features of <strong>MSS</strong> exhibited a noticeable bathochromic shift relative to <strong>SS</strong> in all media. In protic solvents (H₂O, MeOH) and in the solid state, <strong>MSS</strong> is found predominantly in the keto-enamine form, while in aprotic polar solvents (DMSO, DMF), a mixture of keto and enol forms coexist. In contrast, <strong>SS</strong> shows a dynamic coexistence of both tautomeric forms in protic solvents, while the <strong>SS</strong> enol form becomes dominant in DMSO and DMF; in the solid-state <strong>SS</strong> predominantly adopts the keto-enamine form. These differences were rationalized in terms of electronic effects. The direct band gap energies were determined to be 2.75 eV for <strong>SS</strong>, 2.61 eV for <strong>MSS</strong> and 3.03 eV for the <strong>Al(III)/MSS</strong> complex, revealing their wide-band-gap-semiconductor character. These values were supported by DFT calculations, which were found to be able to reproduce the experimental trends and were also used to provide insight into the electronic structure of the studied compounds. Photoluminescence analysis revealed that <strong>MSS</strong> emits in the green region, while the <strong>Al(III)/MSS</strong> complex exhibits a blue-white emission, making both compounds promising candidates for application in single-layer white OLEDs. Additionally, the <strong>Al(III)/MSS</strong> complex displayed photocatalytic activity toward the degradation of methylene blue (MB), with a rate constant of 0.032 min⁻¹, indicating its potential as a multifunctional material for both optoelectronic and environmental applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123014"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734220","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 bis-germylenes stabilized by bis(β-diketiminate) ligands","authors":"Yanling Zhu ,&nbsp;Yufen Yang ,&nbsp;Yi Han,&nbsp;Bin Li","doi":"10.1016/j.ica.2025.123010","DOIUrl":"10.1016/j.ica.2025.123010","url":null,"abstract":"<div><div>Dinuclear germylenes <strong>1</strong> and <strong>2</strong> bearing bis(β-diketiminate) ligands with 1,3-phenylene and 1,2-cyclohexylene linkers, respectively, have been synthesized. The structure flexibility was verified by the variable-temperature NMR analysis. Further salt metathesis with AgOTf led to bis-germylene <strong>3</strong> with OTf substituent. The reaction of <strong>1</strong> with LiAl[OCH(CF₃)₂]₄, aiming to get the dinuclear dication, resulted in the formation of alkoxyl substituted bis-germylene with the elimination of Al[OCH(CF₃)₂]₃. All compounds have been characterized by nuclear magnetic resonance (NMR) and single-crystal X-ray diffraction (SC-XRD).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123010"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734222","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":"Ligand design and catalytic performance of Quinone-oxime copper complexes: role of intramolecular hydrogen bonding","authors":"Vivek Mokashi ,&nbsp;Sourav Datta ,&nbsp;Swapan Patra ,&nbsp;Priyabrata Banerjee ,&nbsp;Sunita Salunke-Gawali","doi":"10.1016/j.ica.2025.123039","DOIUrl":"10.1016/j.ica.2025.123039","url":null,"abstract":"<div><div>Transition metal complexes bearing redox-active ligands often exhibit multiple accessible oxidation states resulting from the electronic interplay between the metal center and the coordinated ligand framework. This study focused on the synthesis and characterization of two mononuclear copper (II) complexes incorporating redox active ligands, 3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one(<strong>LwOx</strong>) and 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (<strong>LwOx-Me</strong>), the ligands differ structurally by the substitution of hydrogen atom with a methyl group in the ligand oxime backbone, this small change affects the ability of the ligand to form intramolecular hydrogen bonds within metal complexes. Remarkably, both metal complexes display multiple redox events attributed to the combined redox-active nature of quinoneoxime-based ligands and the copper(II) center. Furthermore, both complexes were evaluated as catalysts in the oxidation of alcohols. <strong>[Cu(LwOx)</strong>_{<strong>2</strong>}<strong>]</strong> exhibited excellent catalytic activity, whereas <strong>[Cu(LwOx-Me)</strong>_{<strong>2</strong>}<strong>]</strong> showed negligible activity; DFT studies suggest the crucial role of intramolecular hydrogen bonding in modulating the catalytic activity of Cu(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123039"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787876","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":"Magnetic and EPR spectroscopic studies of heterometallic rings featuring {Cr6} chains and rare-earth metal centres","authors":"Yuan Huang ,&nbsp;Grigore A. Timco ,&nbsp;George F.S. Whitehead ,&nbsp;Selena J. Lockyer ,&nbsp;Niklas Geue ,&nbsp;Zhibo Qi ,&nbsp;Adam Brookfield ,&nbsp;Peter Bencok ,&nbsp;Perdita E. Barran ,&nbsp;Nicholas F. Chilton ,&nbsp;Michael L. Baker ,&nbsp;Eric J.L. McInnes ,&nbsp;Richard E.P. Winpenny","doi":"10.1016/j.ica.2025.123037","DOIUrl":"10.1016/j.ica.2025.123037","url":null,"abstract":"<div><div>A rare example of a seven-membered heterometallic ring [Cr^III₆Ce^IIIF₇(O₂C^<em>t</em>Bu)₁₄(THF)₂] (MeCN)₂ (<strong>1</strong>) and five eight-membered heterometallic rings, [^<em>n</em>Pr₂NH₂][Cr^III₆Ln^III₂F₈(O₂C^<em>t</em>Bu)₁₇L_x] (<strong>2</strong>, Ln = Ce, L = HO₂C^<em>t</em>Bu, x = 2, <strong>3</strong>, Ln = Y, L = H₂O, x = 1, <strong>4</strong>, Ln = Gd, L = HO₂C^<em>t</em>Bu, x = 1; <strong>5</strong>, Ln = Tb, L = HO₂C^<em>t</em>Bu, x = 1; <strong>6</strong>, Ln = Yb, no L) have been synthesized and structurally characterized through X-ray diffraction. The structures consist of eight metals in an octagon, with Cr…Cr and Cr…Ln edges bridged by a fluoride and two carboxylates, while the Ln…Ln edges are bridged by a fluoride and three carboxylates. The magnetisation and susceptibility of these compounds were measured using SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy. The magnetic data were fitted with antiferromagnetic exchange interactions between chromium(III) ions, which can be fitted in the {Cr₆Y₂} complex <strong>3</strong> and these parameters were then used to fit the magnetic properties of the {Cr₆Gd₂} complex <strong>4</strong> adding in exchange interactions between the Cr^III and Gd^III The magnetisation and susceptibility below 80 K of <strong>1</strong> and <strong>2</strong> were fitted on the basis of CASSCF-SO calculations at the Ce^III site, and showed a weak ferromagnetic interaction between Cr^III and Ce^III. For <strong>5</strong> and <strong>6</strong> the magnetisation data was fitted by subtracting the data for <strong>3</strong> and treating the residual data as a {Tb₂} and {Yb₂} dimer respectively. The EPR spectra are rich, and for <strong>3</strong> can be modelled as due to <em>S</em> = 1 and <em>S</em> = 2 states of the {Cr₆} chain. The spectra of <strong>1</strong> and <strong>2</strong> are similar, consistent with very weak interactions between the Ce^III and the {Cr₆} chain, while the spectra of <strong>5</strong> and <strong>6</strong> are different to that of <strong>3</strong>, suggesting that the low temperature spectroscopy is due to a spin system in which the Ln^III ions interact with the {Cr₆} chain.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123037"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787882","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":"Advancing anticancer chelation therapy: Insights from enhancing cytotoxic potency, targeted cellular delivery, metal-based immunomodulation, and combinatorial strategies","authors":"Carmen Acosta ,&nbsp;Oscar Claudio-Ares ,&nbsp;Irfan Ullah ,&nbsp;Laura Catalina Cruz ,&nbsp;Adam C. Ducey,&nbsp;Adriana Vidal,&nbsp;Alejandro Escalante-Castaneda,&nbsp;Ambar R. Maldonado-Santos,&nbsp;Biao Liu,&nbsp;Cristina N. Villanueva,&nbsp;Diego A. Martínez-Sebastian,&nbsp;Jubilie Zeda-Rodríguez,&nbsp;Norian Ceballos-Plaza,&nbsp;Sofía V. González-Tossas,&nbsp;Stephanie K. Reyes-Vargas,&nbsp;Wilarye Trujillo-Rivera,&nbsp;Wentao Hou,&nbsp;Yailiz A. Velez-Pizarro,&nbsp;Yiomaris Rodríguez-Manzano,&nbsp;Arthur D. Tinoco","doi":"10.1016/j.ica.2025.123004","DOIUrl":"10.1016/j.ica.2025.123004","url":null,"abstract":"<div><div>Chelation therapy has long been recognized for its success in treating heavy metal poisoning and iron overload disorders. Building on this foundation, drug repurposing of FDA-approved iron chelators for anticancer therapy has been extensively explored, alongside the development of novel agents such as the promising triapine. Current research increasingly targets the essential metals iron, copper, and zinc in oncology, with a focus on chelators that actively modulate the biochemical effects of these metals rather than functioning as ionophores. This review highlights recent advances in refining chelation strategies to enhance cytotoxic potency and tumor specificity, including approaches that tune metal redox activity, synergize with platinum(II)-based drugs, incorporate nanoparticulate delivery systems, leverage metal-driven immunostimulation, and combine with established or emerging therapies. By assessing the successes and limitations of recent studies and surveying relevant human clinical trials, we evaluate the feasibility of integrating chelation therapy into clinical oncology. Evidence suggests that chelation is most effective when combined with other treatment modalities, offering potential synergistic benefits in cancer management.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123004"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683082","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 investigation of dinuclear nickel(II) complexes featuring double-bridging bis(N-heterocyclic carbene) ligands","authors":"Abigail L. Moffett ,&nbsp;Eleanor C. Beams ,&nbsp;Jeffrey D. Zigbuo ,&nbsp;Colin D. McMillen ,&nbsp;Anthony R. Chianese ,&nbsp;Kerry-Ann Green","doi":"10.1016/j.ica.2025.123032","DOIUrl":"10.1016/j.ica.2025.123032","url":null,"abstract":"<div><div>Dinuclear nickel(II) complexes (<strong>4a–4d</strong>) of bidentate propylene-bridged bisbenzimidazolin-2-ylidene ligands are reported. The molecular structures were confirmed by single-crystal X-ray diffraction analysis as 16-membered metallacycles. The double-bridging bidentate bis(N-heterocyclic carbenes) exhibit a <em>trans</em> arrangement to each other about two square planar Ni centers with <em>trans</em> bromide ligands. The molecular structures adopt a stretched-out or open-ring conformation with the absence of any intramolecular Ni···Ni interactions. The complexes are distinguished by the identity of the N-wingtip groups and their benzimidazole backbones. The catalytic activity of the dinuclear complexes (<strong>4a–4d</strong>) and their corresponding monochelate counterparts (<strong>3a–3d</strong>) in the Suzuki-Miyaura coupling and reductive cleavage reactions of aryl sulfamates is discussed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123032"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787877","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":"Rare intermolecular Ni···H anagostic and non-covalent C–H···X (N, S, H) hydrogen bonding interactions assisted supramolecular structure and antimicrobial activity study of Ni(II) cyanodithiocarbimate salts","authors":"Santosh Kumar Singh ,&nbsp;Sudip Mandal ,&nbsp;Utkarsh Talukdar ,&nbsp;Satish Kumar Verma ,&nbsp;Shweta Singh ,&nbsp;Michael G.B. Drew ,&nbsp;Suman Kushwaha","doi":"10.1016/j.ica.2025.123035","DOIUrl":"10.1016/j.ica.2025.123035","url":null,"abstract":"<div><div>In this contribution, four Ni(II) complex salts of the type Z₂ [Ni(L)₂] [Z = (CH₃)₄N⁺ (<strong>1</strong>), (C₂H₅)₄N⁺(<strong>2</strong>), (C₃H₇)₄N⁺(<strong>3</strong>) and (C₅H₁₁)₄N⁺ (<strong>4</strong>); L = Cyanodithiocarbimate NCNCS₂ ²⁻)] have been synthesized. All four salts were characterized by elemental analysis and spectroscopy; while <strong>1</strong> and <strong>3</strong> were further characterized by single-crystal X-ray diffraction analysis. Their crystal structures exhibit sporadic interionic Ni‧‧‧H anagostic contacts, an uncommon feature in complex salts. The interaction energies of the Ni‧‧‧H contacts were evaluated computationally, revealing stronger interactions in <strong>1</strong> than in <strong>3</strong>.</div><div>Crystal packing in all complexes is stabilized by C–H‧‧‧Y (Y<img>H, N, C_sp), S‧‧‧N, C‧‧‧S and S‧‧‧H contacts, in addition to prevailing electrostatic forces. Hirshfeld surface analysis reveals that H‧‧‧H contacts provide the highest contribution among weaker interactions sustaining supramolecular architecture. The antimicrobial activities of complex salts <strong>1–4</strong> were evaluated against <em>Bacillus subtilis</em> (Gram-positive), <em>Shigella boydii</em> (Gram-negative), and the fungi <em>Aspergillus flavus</em> and <em>Fusarium oxysporum</em>. Complexes <strong>1</strong> and <strong>2</strong> have been found to exhibit inhibition efficiencies against <em>B. subtilis</em> comparable to <em>streptomycin</em>, indicating promising potential as alternative antimicrobial agent. Complexes <strong>1</strong> and <strong>2</strong> also inhibited <em>F. oxysporum</em> at 40 μg/disc, whereas <strong>3</strong> and <strong>4</strong> were inactive.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123035"},"PeriodicalIF":3.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787878","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}