Pub Date : 2026-02-01DOI: 10.1016/j.ica.2026.123099
Shafeeq Ur Rehman , Faisal Hayat , Sumaira Khalid , Imen Kebaili , Imed Boukhris , M.S. Al-Buriahi , Ziaur Rehman
To broaden the biological scope of Ni(II) complexes, three new homoleptic Ni(II) complexes, including bis[4-(2-methoxyphen-yl)piperazine-1-carbodithioato-k2S,Sʹ)nickel(II) (1), bis[4-(4-hydroxyphenyl)piperazine-1-car-bodithioato-k2S,Sʹ)nickel(II) (2), and bis(4-dibenzyl- amine-1-carbodithioato-k2S,Sʹ)nickel(II) (3) were synthesized and characterized by elemental and spectroscopic (FTIR, UV–visible and multinuclear NMR) techniques. These techniques and the DFT-based theoretical investigation predicted a pseudo-square planar geometry, and electron density shift towards the nickel center, for 1–3. The DNA binding studies, crucial to gauge the anticancer potential of metallo-drugs, were performed using UV–visible spectroscopy, viscometry, cyclic voltammetry, and molecular docking. The anticancer potential of 1–3 was further assessed computationally by examining their interaction with cancer receptors: Human Epidermal Growth Factor Receptor 2, Epidermal Growth Receptor, and Vascular Endothelial Growth Factor. A positive correlation was noted between the anticancer activity and binding affinity of 1–3 to DNA and cancer receptors. Moreover, these complexes demonstrated considerable potential as antioxidants, antimicrobial and anticancer agents.
{"title":"Monomeric nickel(II) dithiocarbamates: from synthesis to application in the biological domain","authors":"Shafeeq Ur Rehman , Faisal Hayat , Sumaira Khalid , Imen Kebaili , Imed Boukhris , M.S. Al-Buriahi , Ziaur Rehman","doi":"10.1016/j.ica.2026.123099","DOIUrl":"10.1016/j.ica.2026.123099","url":null,"abstract":"<div><div>To broaden the biological scope of Ni(II) complexes, three new homoleptic Ni(II) complexes, including <em>bis</em>[4-(2-methoxyphen-yl)piperazine-1-carbodithioato-k<sup>2</sup>S,Sʹ)nickel(II) <strong>(1)</strong>, <em>bis</em>[4-(4-hydroxyphenyl)piperazine-1-car-bodithioato-k<sup>2</sup>S,Sʹ)nickel(II) (<strong>2</strong>), and <em>bis</em>(4-dibenzyl- amine-1-carbodithioato-k<sup>2</sup>S,Sʹ)nickel(II) (<strong>3</strong>) were synthesized and characterized by elemental and spectroscopic (FTIR, UV–visible and multinuclear NMR) techniques. These techniques and the DFT-based theoretical investigation predicted a pseudo-square planar geometry, and electron density shift towards the nickel center, for <strong>1–3</strong>. The DNA binding studies, crucial to gauge the anticancer potential of metallo-drugs, were performed using UV–visible spectroscopy, viscometry, cyclic voltammetry, and molecular docking. The anticancer potential of <strong>1–3</strong> was further assessed computationally by examining their interaction with cancer receptors: Human Epidermal Growth Factor Receptor 2, Epidermal Growth Receptor, and Vascular Endothelial Growth Factor. A positive correlation was noted between the anticancer activity and binding affinity of <strong>1–3</strong> to DNA and cancer receptors. Moreover, these complexes demonstrated considerable potential as antioxidants, antimicrobial and anticancer agents.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123099"},"PeriodicalIF":3.2,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191001","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 : 2026-02-01DOI: 10.1016/j.ica.2026.123097
Natalia L. Bazyakina , Tatyana S. Koptseva , Mikhail A. Kiskin , Evgeny V. Baranov , Igor L. Fedushkin
The reaction of anionic 1,3-diaza-2-gallols [(ArBIG-bian)Ga][Li(DME)3] (1) and [(ArBIG-bian)Ga][Na(DME)3] (2) (ArBIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with tetrafluoroethylene (1:1) affords oxidative addition of a carbon–fluorine bond to gallium(I) center and the formation of gallium(III) derivatives [(ArBIG-bian)Ga(F)(C2F3)Li(DME)2] (3) and [(ArBIG-bian)Ga(F)(C2F3)Na(DME)2] (4). The reaction of 2 with hexafluorobenzene gives complex [(ArBIG-bian)Ga(F)(C6F5)][Na(DME)3] (5). Compounds 3–5 have been characterized by elemental analysis and IR spectroscopy; their molecular structures have been determined by the single-crystal X-ray analysis. The diamagnetic 3–5 have been characterized by 1H,19F{1H},13C{1H}-NMR spectroscopy.
{"title":"Oxidative addition of carbon–fluorine bonds to the Ga(I) center","authors":"Natalia L. Bazyakina , Tatyana S. Koptseva , Mikhail A. Kiskin , Evgeny V. Baranov , Igor L. Fedushkin","doi":"10.1016/j.ica.2026.123097","DOIUrl":"10.1016/j.ica.2026.123097","url":null,"abstract":"<div><div>The reaction of anionic 1,3-diaza-2-gallols [(Ar<sup>BIG</sup>-bian)Ga][Li(DME)<sub>3</sub>] (<strong>1</strong>) and [(Ar<sup>BIG</sup>-bian)Ga][Na(DME)<sub>3</sub>] (<strong>2</strong>) (Ar<sup>BIG</sup>-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with tetrafluoroethylene (1:1) affords oxidative addition of a carbon–fluorine bond to gallium(I) center and the formation of gallium(III) derivatives [(Ar<sup>BIG</sup>-bian)Ga(F)(C<sub>2</sub>F<sub>3</sub>)Li(DME)<sub>2</sub>] (<strong>3</strong>) and [(Ar<sup>BIG</sup>-bian)Ga(F)(C<sub>2</sub>F<sub>3</sub>)Na(DME)<sub>2</sub>] (<strong>4</strong>). The reaction of <strong>2</strong> with hexafluorobenzene gives complex [(Ar<sup>BIG</sup>-bian)Ga(F)(C<sub>6</sub>F<sub>5</sub>)][Na(DME)<sub>3</sub>] (<strong>5</strong>). Compounds <strong>3</strong>–<strong>5</strong> have been characterized by elemental analysis and IR spectroscopy; their molecular structures have been determined by the single-crystal X-ray analysis. The diamagnetic <strong>3–5</strong> have been characterized by <sup>1</sup>H,<sup>19</sup>F{<sup>1</sup>H},<sup>13</sup>C{<sup>1</sup>H}-NMR spectroscopy.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123097"},"PeriodicalIF":3.2,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191017","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 : 2026-02-01DOI: 10.1016/j.ica.2026.123101
Farha A. Ali , Nahed M.H. Salem , Tarek E. Khalil , Saied M. Soliman , Assem Barakat , Matti Haukka , Ayman El-Faham , Raghdaa A. Massoud
Newly synthesized multidentate s-triazine bis-Schiff base ligand H2L [(3Z,3′E)-3,3′-((6-morpholino-1,3,5-triazine-2,4-diyl)bis(hydrazin-2-yl-1-ylidene))bis(indolin-2-one)] and its three ternary complexes [Ni(L)(Im)2].6H2O; 1, [Mn(L)(Im)2].½Im*3H2O; 2, and [Co(L)(Im)2].½EtOH*H2O; 3 were prepared and thoroughly characterized using spectroscopic methods and theoretical studies. X-ray crystal structure of 1 and 2 complexes revealed that the central metal ion, M(II), is chelated by the dinegative pentadentate (N3O2) ligand (L)−2 and two axially imidazole (Im) groups, resulting in a distorted pentagonal bipyramidal geometry. In contrast, in complex 3, Co(II) is bound to a dinegative tetradentate (N3O) (L)−2 ligand and two axial imidazole moieties forming a distorted octahedral geometry. Hirshfeld surface and energy framework analyses revealed that dispersion forces dominate the supramolecular architecture of complexes 1 and 2 (Edis= − 303.494 and − 215.880 kJ/mol, respectively), whereas in 3, electrostatic force (Eele = −376.215 kJ/mol) plays the primary role. Atoms in molecules calculations (AIM) indicate that most of M-O and M-N bonds in 1 exhibit covalent character, whereas those in 2 and 3 reveal mostly closed-shell nature. Moreover, the charge of central Ni(II), Mn(II), and Co(II) are reduced upon complexation with ligand units to 0.8326, 1.0526, and 0.8564e for 1, 2, and 3, respectively. Biological evaluation demonstrated that 1 and 3 showed greater activity compared to the free ligand against Gram-positive and Gram-negative bacteria. Notably, their activity against S. aureus was similar to the reference gentamicin, producing a 20 mm inhibition zone and a minimum inhibitory concentration (MIC) of 213–217 μM. Safety evaluation of the studied compounds indicated no cytotoxic impact on normal lung fibroblast WI-38 cell line.
{"title":"Design, synthesis, structural and supramolecular insights of Ni(II), Co(II), and Mn(II) ternary imidazole complexes with Giant s-triazine ligand bearing Isatin arms","authors":"Farha A. Ali , Nahed M.H. Salem , Tarek E. Khalil , Saied M. Soliman , Assem Barakat , Matti Haukka , Ayman El-Faham , Raghdaa A. Massoud","doi":"10.1016/j.ica.2026.123101","DOIUrl":"10.1016/j.ica.2026.123101","url":null,"abstract":"<div><div>Newly synthesized multidentate <em>s</em>-triazine <em>bis</em>-Schiff base ligand <strong>H</strong><sub><strong>2</strong></sub><strong>L</strong> [(3<em>Z</em>,3′<em>E</em>)-3,3′-((6-morpholino-1,3,5-triazine-2,4-diyl)<em>bis</em>(hydrazin-2-yl-1-ylidene))<em>bis</em>(indolin-2-one)] and its three ternary complexes [Ni(<strong>L</strong>)(Im)<sub>2</sub>].6H<sub>2</sub>O; <strong>1</strong>, [Mn(<strong>L</strong>)(Im)<sub>2</sub>].½Im*3H<sub>2</sub>O; <strong>2</strong>, and [Co(<strong>L</strong>)(Im)<sub>2</sub>].½EtOH*H<sub>2</sub>O; <strong>3</strong> were prepared and thoroughly characterized using spectroscopic methods and theoretical studies. X-ray crystal structure of <strong>1</strong> and <strong>2</strong> complexes revealed that the central metal ion, M(II), is chelated by the dinegative pentadentate (N3O2) ligand (<strong>L</strong>)<sup>−2</sup> and two axially imidazole (Im) groups, resulting in a distorted pentagonal bipyramidal geometry. In contrast, in complex <strong>3,</strong> Co(II) is bound to a dinegative tetradentate (N3O) (<strong>L</strong>)<sup><strong>−2</strong></sup> ligand and two axial imidazole moieties forming a distorted octahedral geometry. Hirshfeld surface and energy framework analyses revealed that dispersion forces dominate the supramolecular architecture of complexes <strong>1</strong> and <strong>2</strong> (E<sub>dis=</sub> − 303.494 and − 215.880 kJ/mol, respectively), whereas in <strong>3</strong>, electrostatic force (E<sub>ele</sub> = −376.215 kJ/mol) plays the primary role. Atoms in molecules calculations (AIM) indicate that most of M-O and M-N bonds in <strong>1</strong> exhibit covalent character, whereas those in <strong>2</strong> and <strong>3</strong> reveal mostly closed-shell nature. Moreover, the charge of central Ni(II), Mn(II), and Co(II) are reduced upon complexation with ligand units to 0.8326, 1.0526, and 0.8564e for <strong>1</strong>, <strong>2</strong>, and <strong>3</strong>, respectively. Biological evaluation demonstrated that <strong>1</strong> and <strong>3</strong> showed greater activity compared to the free ligand against Gram-positive and Gram-negative bacteria. Notably, their activity against <em>S. aureus</em> was similar to the reference gentamicin, producing a 20 mm inhibition zone and a minimum inhibitory concentration (MIC) of 213–217 μM. Safety evaluation of the studied compounds indicated no cytotoxic impact on normal lung fibroblast WI-38 cell line.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123101"},"PeriodicalIF":3.2,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191015","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 low-molecular-weight gelator, ((2-hydroxynaphthalen-1-yl)methyl)-L-threonine (H3L), has been synthesized and characterized. The ligand H3L has been used to synthesize a copper metal-organic hydrogel, Cu-MOG. The hydrogel has been characterized by matrix-assisted laser desorption/ionization – time of flight (MALDI- TOF) mass spectrometry, IR and X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and rheological measurements, and microscopic techniques, like field emission scanning microscopy (FESEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The hydrogel has been utilized as a heterogeneous and reusable catalyst for the reaction of CS2and CO2with epoxides, producing 1,3-oxathiolane-2-thiones and cyclic carbonates, respectively.
合成了一种低分子量的凝胶（（2-羟基萘-1-基）甲基）- l -苏氨酸（H3L）。用配体H3L合成了铜金属有机水凝胶Cu-MOG。通过基质辅助激光解吸/电离飞行时间（MALDI- TOF）质谱、红外和x射线光电子能谱（XPS）、粉末x射线衍射（PXRD）、热重分析（TGA）、流变学测量以及场发射扫描显微镜（FESEM）、透射电子显微镜（TEM）和原子力显微镜（AFM）等显微技术对水凝胶进行了表征。该水凝胶作为一种多相可重复使用的催化剂，用于CS2和CO2与环氧化物的反应，分别生成1,3-草硫烷-2-硫酮和环碳酸盐。
{"title":"A copper metal – Organic hydrogel as a heterogeneous reusable catalyst for the cycloaddition of CS2 and CO2 with epoxide","authors":"Mahesh Samanta, Tapas Mahata, Manish Bhattacharjee","doi":"10.1016/j.ica.2026.123091","DOIUrl":"10.1016/j.ica.2026.123091","url":null,"abstract":"<div><div>A low-molecular-weight gelator<strong>, ((2-hydroxynaphthalen-1-yl)methyl)-L-threonine (H</strong><sub><strong>3</strong></sub><strong>L), has been synthesized and characterized.</strong> The ligand <strong>H</strong><sub><strong>3</strong></sub><strong>L has been used to synthesize a copper metal-organic hydrogel, Cu-MOG. The hydrogel has been characterized by matrix-assisted laser desorption/ionization – time of flight (MALDI- TOF) mass spectrometry, IR and X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD),</strong> thermogravimetric analysis (TGA), and rheological measurements, and microscopic techniques, <strong>like field emission scanning microscopy (FESEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The hydrogel has been utilized as a heterogeneous and reusable catalyst for the reaction of CS</strong><sub><strong>2</strong></sub> <strong>and CO</strong><sub><strong>2</strong></sub> <strong>with epoxides, producing 1,3-oxathiolane-2-thiones and cyclic carbonates, respectively.</strong></div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"596 ","pages":"Article 123091"},"PeriodicalIF":3.2,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146162054","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 : 2026-01-30DOI: 10.1016/j.ica.2026.123075
Diksha U. Sawant, David R. Turner
Chiral and racemic forms of a urea–thiazole-based ligand (R-L and rac-L) form anion-dependent solid-state structures when reacted with a range of silver(I) salts. A combination of hydrogen bonds from the urea groups of the ligands and metal-anion interactions drive these assemblies, alongside argentophilic and π-π interactions. A systematic investigation using a range of counter anions (benzoate, nitrate, sulfate, triflate, tetrafluoroborate, trifluoroacetate) produced a family of crystalline materials, including monomeric and dimeric tweezer-like complexes and one-dimensional coordination polymers with a clear dependence on the nature of the anion. Comparison of racemic and enantiopure systems highlights the influence of chirality on supramolecular packing and intermolecular hydrogen bonding. The influence of the anion, in terms of geometry and coordinating ability, shows a preference for dimeric assemblies with carboxylate and nitrate and only mononuclear complexes with traditionally “weaker” anions.
{"title":"Influence of anion on the solid-state assembly of dimeric tweezer complexes","authors":"Diksha U. Sawant, David R. Turner","doi":"10.1016/j.ica.2026.123075","DOIUrl":"10.1016/j.ica.2026.123075","url":null,"abstract":"<div><div>Chiral and racemic forms of a urea–thiazole-based ligand (<em>R</em>-L and <em>rac</em>-L) form anion-dependent solid-state structures when reacted with a range of silver(I) salts. A combination of hydrogen bonds from the urea groups of the ligands and metal-anion interactions drive these assemblies, alongside argentophilic and π-π interactions. A systematic investigation using a range of counter anions (benzoate, nitrate, sulfate, triflate, tetrafluoroborate, trifluoroacetate) produced a family of crystalline materials, including monomeric and dimeric tweezer-like complexes and one-dimensional coordination polymers with a clear dependence on the nature of the anion. Comparison of racemic and enantiopure systems highlights the influence of chirality on supramolecular packing and intermolecular hydrogen bonding. The influence of the anion, in terms of geometry and coordinating ability, shows a preference for dimeric assemblies with carboxylate and nitrate and only mononuclear complexes with traditionally “weaker” anions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123075"},"PeriodicalIF":3.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191018","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 : 2026-01-28DOI: 10.1016/j.ica.2026.123096
Matthew J. Evans, Jeremy C. Mullins, Cameron Jones
The synthesis of alkali metal magnesiates M[Mg(NONTCHP)(HMDS)] (M = K, Rb or Cs; HMDS = bis(trimethylsilyl)amide; NONTCHP = 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) via coordination of [Mg(NONTCHP)] with M(HMDS) is reported. Each complex is characterised using single crystal X-ray diffraction measurements and NMR spectroscopic methods. In the solid-state, each system exists as a 1D-polymer that assembles via bridging M‧‧‧π(arene) interactions to two [Mg(NONTCHP)(HMDS)]− units. For K[Mg(NONTCHP)(HMDS)], polymerization occurs via coordination of each K-center to TCHP and xanthene arene rings. In contrast, for the heavier group 1 magnesiates, Rb[Mg(NONTCHP)(HMDS)] and Cs[Mg(NONTCHP)(HMDS)], the alkali metals exhibit alternating xanthene, xanthene- and TCHP, TCHP-coordination along the polymer chain. This work highlights the influence that group 1 metal cations can have on the long-range structure of bis(anilido)xanthene magnesiate complexes.
{"title":"Structural diversity in heavier alkali metal salts of a heteroleptic magnesium triamide anion","authors":"Matthew J. Evans, Jeremy C. Mullins, Cameron Jones","doi":"10.1016/j.ica.2026.123096","DOIUrl":"10.1016/j.ica.2026.123096","url":null,"abstract":"<div><div>The synthesis of alkali metal magnesiates M[Mg(NON<sup>TCHP</sup>)(HMDS)] (M = K, Rb or Cs; HMDS = bis(trimethylsilyl)amide; NON<sup>TCHP</sup> = 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) <em>via</em> coordination of [Mg(NON<sup>TCHP</sup>)] with M(HMDS) is reported. Each complex is characterised using single crystal X-ray diffraction measurements and NMR spectroscopic methods. In the solid-state, each system exists as a 1D-polymer that assembles <em>via</em> bridging M‧‧‧π(arene) interactions to two [Mg(NON<sup>TCHP</sup>)(HMDS)]<sup>−</sup> units. For K[Mg(NON<sup>TCHP</sup>)(HMDS)], polymerization occurs <em>via</em> coordination of each K-center to TCHP and xanthene arene rings. In contrast, for the heavier group 1 magnesiates, Rb[Mg(NON<sup>TCHP</sup>)(HMDS)] and Cs[Mg(NON<sup>TCHP</sup>)(HMDS)], the alkali metals exhibit alternating xanthene, xanthene- and TCHP, TCHP-coordination along the polymer chain. This work highlights the influence that group 1 metal cations can have on the long-range structure of bis(anilido)xanthene magnesiate complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123096"},"PeriodicalIF":3.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077052","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 : 2026-01-28DOI: 10.1016/j.ica.2026.123098
Sudeep Ranjan Jana , Koushik Saha , Arabinda Chakraborty , Ananya Das Mahapatra , Sukanya Paul , Indrajit Saha , Chittaranjan Sinha
A pyridylhydrazide Schiff base, N’-(2-hydroxy-4,6-dimethoxybenzylidene) picolinohydrazide (H₂L) has been comprehensively characterized by spectroscopic and single crystal X-ray diffraction data. H2L is weakly emissive and shows fluorescence enhancement selectively in CH3CN/H2O (1:99, v/v; HEPES Buffer, pH 7.2) medium for Al3+ ion in presence of fifteen other cations (Na+, K+, Ca2+, Mg2+, Cr3+, Hg2+, Cu2+, Pb2+, Pd2+, Ba2+, Zn2+, Fe3+, Co2+, Ni2+, Cd2+, Ga3+ and In3+) with limit of detection (LOD) 1.32 nM. The probe also shows colour change from colourless to yellow in the CH3CN solution only for CN− in presence of eighteen anions (F−, Cl−, Br−, I−, NO₃−, NO₂−, HSO₄−, SO₄2−, H₂PO₄−, HPO₄2−, ClO₄−, SCN−, OCN−, S₂O₃2−, AsO₂−, AsO₄3−, HF₂−, N₃−) with LOD 0.367 μM. The binding of H₂L separately with Al3+ and CN− was supported by 1H NMR spectral titration, IR spectra and Job's Plot analysis revealed 1:1 stoichiometry [H₂LAl3+] and [H₂L + CN−]. The probe was also applied for quantitative analysis of Al3+ in pharmaceutical samples (Telma, Nexpro, Diovol, Disprin, Diagene) while H2L absorbed paper strips facilitated rapid on-site detection of Al3+ (fluorogenic) and CN− (chromogenic) underscoring its potential use for practical application. Theoretical insights into the electronic transitions were obtained from DFT studies through geometrical optimization of the probe in complexation with Al3+ and CN−.
{"title":"Pyridyl hydrazide Schiff base: Structure, spectra, Fluorogenic Al3+ and chromogenic CN− sensors and theoretical interpretation","authors":"Sudeep Ranjan Jana , Koushik Saha , Arabinda Chakraborty , Ananya Das Mahapatra , Sukanya Paul , Indrajit Saha , Chittaranjan Sinha","doi":"10.1016/j.ica.2026.123098","DOIUrl":"10.1016/j.ica.2026.123098","url":null,"abstract":"<div><div>A pyridylhydrazide Schiff base, N’-(2-hydroxy-4,6-dimethoxybenzylidene) picolinohydrazide (H₂L) has been comprehensively characterized by spectroscopic and single crystal X-ray diffraction data. H<sub>2</sub>L is weakly emissive and shows fluorescence enhancement selectively in CH<sub>3</sub>CN/H<sub>2</sub>O (1:99, <em>v</em>/v; HEPES Buffer, pH 7.2) medium for Al<sup>3+</sup> ion in presence of fifteen other cations (Na<sup>+</sup>, K<sup>+</sup>, Ca<sup>2+</sup>, Mg<sup>2+</sup>, Cr<sup>3+</sup>, Hg<sup>2+</sup>, Cu<sup>2+</sup>, Pb<sup>2+</sup>, Pd<sup>2+</sup>, Ba<sup>2+</sup>, Zn<sup>2+</sup>, Fe<sup>3+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>, Cd<sup>2+</sup>, Ga<sup>3+</sup> and In<sup>3+</sup>) with limit of detection (LOD) 1.32 nM. The probe also shows colour change from colourless to yellow in the CH<sub>3</sub>CN solution only for CN<sup>−</sup> in presence of eighteen anions (F<sup>−</sup>, Cl<sup>−</sup>, Br<sup>−</sup>, I<sup>−</sup>, NO₃<sup>−</sup>, NO₂<sup>−</sup>, HSO₄<sup>−</sup>, SO₄<sup>2−</sup>, H₂PO₄<sup>−</sup>, HPO₄<sup>2−</sup>, ClO₄<sup>−</sup>, SCN<sup>−</sup>, OCN<sup>−</sup>, S₂O₃<sup>2−</sup>, AsO₂<sup>−</sup>, AsO₄<sup>3−</sup>, HF₂<sup>−</sup>, N₃<sup>−</sup>) with LOD 0.367 μM. The binding of H₂L separately with Al<sup>3+</sup> and CN<sup>−</sup> was supported by <sup>1</sup>H NMR spectral titration, IR spectra and Job's Plot analysis revealed 1:1 stoichiometry [H₂L<img>Al<sup>3+</sup>] and [H₂L + CN<sup>−</sup>]. The probe was also applied for quantitative analysis of Al<sup>3+</sup> in pharmaceutical samples (Telma, Nexpro, Diovol, Disprin, Diagene) while H<sub>2</sub>L absorbed paper strips facilitated rapid on-site detection of Al<sup>3+</sup> (fluorogenic) and CN<sup>−</sup> (chromogenic) underscoring its potential use for practical application. Theoretical insights into the electronic transitions were obtained from DFT studies through geometrical optimization of the probe in complexation with Al<sup>3+</sup> and CN<sup>−</sup>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123098"},"PeriodicalIF":3.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077053","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 : 2026-01-28DOI: 10.1016/j.ica.2026.123092
Jiao Guo , Xin-Hong Li , Ya-Kun Zhang , Wei Zhang , Ai-Min Chen , Yuan-Chun He
Coordination polymers (CPs) have garnered significant attention due to their structural diversity and functional versatility, driven by the reasonable selection of metal centers and organic ligands. In this work, we synthesizes and characterizes four new Ni(II)-based CPs based on 1-(3-carboxybenzyl)-1H-pyrazole-4-carboxylic acid (H2CBPC) and auxiliary N-donor ligands. The structures were determined by single-crystal X-ray diffraction and exhibit diversity influenced by ligand coordination modes, the presence of auxiliary N-donor ligands, and weak interactions. Hirshfeld surface analyses quantified intermolecular interactions, highlighting the role of non-covalent forces in stabilizing supramolecular architectures. Furthermore, compounds 1–4 were investigated as anode materials for lithium-ion batteries. The charge-discharge curves, cycling performance, and rate capability of these four compounds have been thoroughly tested. All charge-discharge curves demonstrate poor specific capacity, while cycling tests and rate capability assessments indicate reasonable cycling stability. While they do not exhibit particularly outstanding performance compared to other materials, the results still offer valuable insights for the development of lithium-ion battery anodes.
{"title":"Ligand-directed assembly of four new Ni(II)-based coordination polymers: structures, Hirshfeld surface analyses and electrochemical properties","authors":"Jiao Guo , Xin-Hong Li , Ya-Kun Zhang , Wei Zhang , Ai-Min Chen , Yuan-Chun He","doi":"10.1016/j.ica.2026.123092","DOIUrl":"10.1016/j.ica.2026.123092","url":null,"abstract":"<div><div>Coordination polymers (CPs) have garnered significant attention due to their structural diversity and functional versatility, driven by the reasonable selection of metal centers and organic ligands. In this work, we synthesizes and characterizes four new Ni(II)-based CPs based on 1-(3-carboxybenzyl)-1H-pyrazole-4-carboxylic acid (H<sub>2</sub>CBPC) and auxiliary N-donor ligands. The structures were determined by single-crystal X-ray diffraction and exhibit diversity influenced by ligand coordination modes, the presence of auxiliary N-donor ligands, and weak interactions. Hirshfeld surface analyses quantified intermolecular interactions, highlighting the role of non-covalent forces in stabilizing supramolecular architectures. Furthermore, compounds <strong>1</strong>–<strong>4</strong> were investigated as anode materials for lithium-ion batteries. The charge-discharge curves, cycling performance, and rate capability of these four compounds have been thoroughly tested. All charge-discharge curves demonstrate poor specific capacity, while cycling tests and rate capability assessments indicate reasonable cycling stability. While they do not exhibit particularly outstanding performance compared to other materials, the results still offer valuable insights for the development of lithium-ion battery anodes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123092"},"PeriodicalIF":3.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077054","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 : 2026-01-27DOI: 10.1016/j.ica.2026.123095
Zhengting Wang , Ying Zhang , Rui Gao , Xiao Xiao , Wen Ge , Qihang Zhou , Shukang Deng , Junjie Li
A three–dimensional porous CoFeSe2 bimetallic selenide catalyst was prepared via an electrodeposition–hydrothermal selenization method. During electrochemical activation, CoFeSe₂ undergoes in-situ surface reconstruction to form se–co(OH)₂–Fe, which serves as the actual catalytically active phase. The oxygen evolution reaction (OER) activity and mechanism were systematically evaluated. XRD, XPS, and HAADF–STEM indicate that co, Fe, and se are uniformly distributed in CoFeSe2, forming abundant metal–selenide coordination interfaces. Electrochemical measurements show that the activated se–co(OH)₂–Fe requires an overpotential of only 206 mV to reach a current density of 10 mA cm−2 in 1 M KOH, delivers a low Tafel slope of 24.3 mV dec−1, and can operate stably at an industrial–level current density of 200 mA cm−2 for 130 h with the overpotential increasing by only 1.2%. Electrochemical probe experiments reveal the incorporation of Fe into the co-based framework activates the lattice oxygen oxidation mechanism (LOM), breaking the linear constraints of the traditional adsorbate evolution mechanism (AEM), while the introduction of se enhances reaction kinetics by optimizing electronic conductivity. This work provides a new strategy for regulating electronic structure and reaction pathways to design efficient and durable noble–metal–free OER catalysts
采用电沉积-水热硒化法制备了三维多孔CoFeSe2双金属硒化催化剂。在电化学活化过程中，CoFeSe₂经过原位表面重构形成se-co (OH) 2 -Fe，这是实际的催化活性相。系统评价了析氧反应（OER）活性及其机理。XRD、XPS和HAADF-STEM表明co、Fe和se在CoFeSe2中均匀分布，形成丰富的金属-硒化物配位界面。电化学测量表明，在1 M KOH条件下，活化的se-co (OH) 2 -Fe仅需206 mV过电位即可达到10 mA cm - 2的电流密度，Tafel斜率较低，为24.3 mV dec - 1，可在200 mA cm - 2的工业级电流密度下稳定工作130 h，过电位仅增加1.2%。电化学探针实验表明，Fe加入到co基框架中激活了晶格氧氧化机制（LOM），打破了传统吸附物演化机制（AEM）的线性约束，而se的引入通过优化电子电导率增强了反应动力学。这项工作为设计高效耐用的无贵金属OER催化剂提供了调控电子结构和反应途径的新策略
{"title":"Surface reconstruction of bimetallic selenide enables lattice oxygen activation for efficient oxygen evolution reaction","authors":"Zhengting Wang , Ying Zhang , Rui Gao , Xiao Xiao , Wen Ge , Qihang Zhou , Shukang Deng , Junjie Li","doi":"10.1016/j.ica.2026.123095","DOIUrl":"10.1016/j.ica.2026.123095","url":null,"abstract":"<div><div>A three–dimensional porous CoFeSe<sub>2</sub> bimetallic selenide catalyst was prepared via an electrodeposition–hydrothermal selenization method. During electrochemical activation, CoFeSe₂ undergoes in-situ surface reconstruction to form se<span>–</span>co(OH)₂<span>–</span>Fe, which serves as the actual catalytically active phase. The oxygen evolution reaction (OER) activity and mechanism were systematically evaluated. XRD, XPS, and HAADF–STEM indicate that co, Fe, and se are uniformly distributed in CoFeSe<sub>2</sub>, forming abundant metal–selenide coordination interfaces. Electrochemical measurements show that the activated se–co(OH)₂<span>–</span>Fe requires an overpotential of only 206 mV to reach a current density of 10 mA cm<sup>−2</sup> in 1 M KOH, delivers a low Tafel slope of 24.3 mV dec<sup>−1</sup>, and can operate stably at an industrial–level current density of 200 mA cm<sup>−2</sup> for 130 h with the overpotential increasing by only 1.2%. Electrochemical probe experiments reveal the incorporation of Fe into the co-based framework activates the lattice oxygen oxidation mechanism (LOM), breaking the linear constraints of the traditional adsorbate evolution mechanism (AEM), while the introduction of se enhances reaction kinetics by optimizing electronic conductivity. This work provides a new strategy for regulating electronic structure and reaction pathways to design efficient and durable noble–metal–free OER catalysts</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123095"},"PeriodicalIF":3.2,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077055","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 : 2026-01-27DOI: 10.1016/j.ica.2026.123094
Fu-Lin Mao
An aroylhydrazone compound N′-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide (H2L) was prepared and characterized by IR, UV–Vis, 1H and 13C NMR spectra. Reaction of H2L with copper nitrate, cobalt nitrate and zinc iodide, respectively, afforded three new complexes [Cu2(HL)2(ONO2)2]∙2H2O (1∙2H2O), [Co2L2(EtOH)2(OH2)2]2NO3 (2), and [Zn2I2(HL)2]∙2EtOH (3∙2EtOH). The complexes have been characterized by IR and UV–Vis spectra. Structures of H2L and the complexes were further confirmed by single crystal X-ray determination. H2L crystallizes in monoclinic system space group P21/c, and the three complexes in triclinic P-1. Single crystal X-ray diffraction analysis reveals that the Cu atoms in 1 and Zn atoms in 3 are in square pyramidal coordination, and the Co atoms in 2 are in octahedral coordination. The compounds were assayed against the bacterial strains Bacillus subtillis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aereuguinosa. The Cu and Zn complexes have effective antibacterial activities.
{"title":"Synthesis, characterization and crystal structures of N′-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide and it's copper(II), cobalt(III) and zinc(II) complexes with antibacterial activity","authors":"Fu-Lin Mao","doi":"10.1016/j.ica.2026.123094","DOIUrl":"10.1016/j.ica.2026.123094","url":null,"abstract":"<div><div>An aroylhydrazone compound <em>N′</em>-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide (H<sub>2</sub>L) was prepared and characterized by IR, UV–Vis, <sup>1</sup>H and <sup>13</sup>C NMR spectra. Reaction of H<sub>2</sub>L with copper nitrate, cobalt nitrate and zinc iodide, respectively, afforded three new complexes [Cu<sub>2</sub>(HL)<sub>2</sub>(ONO<sub>2</sub>)<sub>2</sub>]∙2H<sub>2</sub>O (<strong>1</strong>∙2H<sub>2</sub>O), [Co<sub>2</sub>L<sub>2</sub>(EtOH)<sub>2</sub>(OH<sub>2</sub>)<sub>2</sub>]2NO<sub>3</sub> (<strong>2</strong>), and [Zn<sub>2</sub>I<sub>2</sub>(HL)<sub>2</sub>]∙2EtOH (<strong>3</strong>∙2EtOH). The complexes have been characterized by IR and UV–Vis spectra. Structures of H<sub>2</sub>L and the complexes were further confirmed by single crystal X-ray determination. H<sub>2</sub>L crystallizes in monoclinic system space group <em>P</em>2<sub>1</sub>/<em>c</em>, and the three complexes in triclinic <em>P</em>-1. Single crystal X-ray diffraction analysis reveals that the Cu atoms in <strong>1</strong> and Zn atoms in <strong>3</strong> are in square pyramidal coordination, and the Co atoms in <strong>2</strong> are in octahedral coordination. The compounds were assayed against the bacterial strains <em>Bacillus subtillis</em>, <em>Staphylococcus aureus</em>, <em>Escherichia coli</em>, and <em>Pseudomonas aereuguinosa</em>. The Cu and Zn complexes have effective antibacterial activities.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123094"},"PeriodicalIF":3.2,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074531","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}
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