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}
Pub Date : 2026-01-24DOI: 10.1016/j.ica.2026.123093
Jie Zhao , Jin-Song Li , Wei-Yu Zou , Ju-Wen Zhang , Bin-Qiu Liu , Xi-Qiang Tian
Under solvothermal conditions of CH3CH2OH and H2O, a series of rare earth-organic complexes [Ln(3,5-DCB)3(dmbpy)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Er (7) and Yb (8), 3,5-HDCB = 3,5-dichlorobenzoic acid, dmbpy = 4,4′-dimethyl-2,2′-bipyridine] have been synthesized by the reactions of Ln(NO3)3·6H2O with 3,5-HDCB, dmbpy and NaOH. These complexes were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), elemental analysis (EA), fourier transform infrared (FT-IR) spectrometer, thermogravimetric analysis (TGA) and differential thermoanalysis (DTA). The SCXRD analysis reveals complexes 1–8 exhibit two sorts of distinct structures. Complex 1 features a one-dimensional (1D) chain structure, and the adjacent chains are interconnected through the π–π interactions between the dmbpy co-ligands to generate a two-dimensional (2D) supramolecular layer. Complexes 2–8 possess discrete dinuclear cluster structures, which can be extended into a three-dimensional (3D) supramolecular framework by the π–π interactions. The fluorescence and fluorescence lifetimes of 2, 3, 5 and 6 were studied and the characteristic emission spectra of rare earth ions are observed. The magnetic investigation of 1 and 4–8 was conducted and complex 6 displays a slow magnetic relaxation behavior.
{"title":"Synthesis, characterization and properties of a series of rare earth 3,5-dichlorobenzoate complexes including 4,4′-dimethyl-2,2′-bipyridine","authors":"Jie Zhao , Jin-Song Li , Wei-Yu Zou , Ju-Wen Zhang , Bin-Qiu Liu , Xi-Qiang Tian","doi":"10.1016/j.ica.2026.123093","DOIUrl":"10.1016/j.ica.2026.123093","url":null,"abstract":"<div><div>Under solvothermal conditions of CH<sub>3</sub>CH<sub>2</sub>OH and H<sub>2</sub>O, a series of rare earth-organic complexes [Ln(3,5-DCB)<sub>3</sub>(dmbpy)] [Ln = Nd (<strong>1</strong>), Sm (<strong>2</strong>), Eu (<strong>3</strong>), Gd (<strong>4</strong>), Tb (<strong>5</strong>), Dy (<strong>6</strong>), Er (<strong>7</strong>) and Yb (<strong>8</strong>), 3,5-HDCB = 3,5-dichlorobenzoic acid, dmbpy = 4,4′-dimethyl-2,2′-bipyridine] have been synthesized by the reactions of Ln(NO<sub>3</sub>)<sub>3</sub>·6H<sub>2</sub>O with 3,5-HDCB, dmbpy and NaOH. These complexes were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), elemental analysis (EA), fourier transform infrared (FT-IR) spectrometer, thermogravimetric analysis (TGA) and differential thermoanalysis (DTA). The SCXRD analysis reveals complexes <strong>1</strong>–<strong>8</strong> exhibit two sorts of distinct structures. Complex <strong>1</strong> features a one-dimensional (1D) chain structure, and the adjacent chains are interconnected through the π–π interactions between the dmbpy co-ligands to generate a two-dimensional (2D) supramolecular layer. Complexes <strong>2</strong>–<strong>8</strong> possess discrete dinuclear cluster structures, which can be extended into a three-dimensional (3D) supramolecular framework by the π–π interactions. The fluorescence and fluorescence lifetimes of <strong>2</strong>, <strong>3</strong>, <strong>5</strong> and <strong>6</strong> were studied and the characteristic emission spectra of rare earth ions are observed. The magnetic investigation of <strong>1</strong> and <strong>4</strong>–<strong>8</strong> was conducted and complex <strong>6</strong> displays a slow magnetic relaxation behavior.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123093"},"PeriodicalIF":3.2,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The fabrication of bimetallic metal-organic frameworks (MOFs) has emerged as an effective strategy for enhancing both structural stability and catalytic efficiency. In this study, we report the solvothermal synthesis of a zirconium-based framework, Zr@BDC@Fc-MOF, incorporating ferrocene units into the structure. The redox-active ferrocene moieties impart additional functionality, while the Zr-BDC network provides porosity and stability, resulting in a material with improved catalytic properties. The framework was characterized by FT-IR, FE-SEM with EDS mapping, P-XRD, XPS, BET, and TEM, confirming its crystallinity and well-developed porous structure. Zr@BDC@Fc-MOF was subsequently employed as a heterogeneous catalyst for the synthesis of 2-amino-3-cyanopyridine derivatives, affording products in good to excellent yield under ambient conditions. The catalyst exhibited durability and specific catalytic activity, highlighting its potential as a promising platform for sustainable heterocycles synthesis.
{"title":"Sustainable catalysis via ferrocene-modified Zr-MOF for solvent-free annulations toward functionalized pyridine heterocycles","authors":"Lokesh Mahavar, Parveen Kumar, Gourav Kumar, Meena Nemiwal","doi":"10.1016/j.ica.2026.123090","DOIUrl":"10.1016/j.ica.2026.123090","url":null,"abstract":"<div><div>The fabrication of bimetallic metal-organic frameworks (MOFs) has emerged as an effective strategy for enhancing both structural stability and catalytic efficiency. In this study, we report the solvothermal synthesis of a zirconium-based framework, Zr@BDC@Fc-MOF, incorporating ferrocene units into the structure. The redox-active ferrocene moieties impart additional functionality, while the Zr-BDC network provides porosity and stability, resulting in a material with improved catalytic properties. The framework was characterized by FT-IR, FE-SEM with EDS mapping, P-XRD, XPS, BET, and TEM, confirming its crystallinity and well-developed porous structure. Zr@BDC@Fc-MOF was subsequently employed as a heterogeneous catalyst for the synthesis of 2-amino-3-cyanopyridine derivatives, affording products in good to excellent yield under ambient conditions. The catalyst exhibited durability and specific catalytic activity, highlighting its potential as a promising platform for sustainable heterocycles synthesis.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123090"},"PeriodicalIF":3.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074532","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}
N-Acylthiourea derivatives bearing a piperazinyl group are valuable anticancer scaffolds due to their structural versatility, favorable physicochemical properties, and ability to interact with multiple cancer-related biological targets. They are considered promising leads for developing new chemotherapeutic agents. In this study, ten ligands were synthesized in our laboratory and evaluated for their cytotoxic activity against HCT116 colon carcinoma cells. Building on these findings, we designed and computationally modeled novel copper(I) complexes of the ligands as potential inhibitors of cyclin-dependent kinase 2 (CDK2), a well-established therapeutic target in colorectal cancer. A comprehensive in silico approach was employed, including molecular docking, ADMET prediction, and drug-likeness evaluation. The ligands and their copper(I) complexes were docked against the CDK2 crystal structure (PDB ID: 2VTO), and binding affinities were assessed. Before docking, all compounds were geometry optimized, and their electronic properties, such as total energy and HOMO/LUMO orbital distributions, were calculated to inform docking simulations. ProTox 3.0 predicted all compounds to be non-toxic across major endpoints, with inactivity probabilities ranging from 0.50 to 0.99. The results suggest that both the free ligands and their copper complexes exhibit favorable binding interactions with the CDK2 active site, supporting their potential as lead compounds for further development in colon cancer therapeutics. Molecular dynamics simulations using the selected OPLS-AA force field were performed to analyze RMSD, RMSF, and protein–ligand contacts for the best docking poses.
{"title":"Computational insights into thiourea derivatives and their copper complexes as potential CDK inhibitors in HCT116 colon carcinoma cells","authors":"Rahime Eshaghi Malekshah , Amir Karim , Jebiti Haribabu , Anantha Krishnan Dhanabalan , Daniel Moraga , Najeeb Ullah , Sodio C.N. Hsu","doi":"10.1016/j.ica.2026.123087","DOIUrl":"10.1016/j.ica.2026.123087","url":null,"abstract":"<div><div><em>N-</em>Acylthiourea derivatives bearing a piperazinyl group are valuable anticancer scaffolds due to their structural versatility, favorable physicochemical properties, and ability to interact with multiple cancer-related biological targets. They are considered promising leads for developing new chemotherapeutic agents. In this study, ten ligands were synthesized in our laboratory and evaluated for their cytotoxic activity against HCT116 colon carcinoma cells. Building on these findings, we designed and computationally modeled novel copper(I) complexes of the ligands as potential inhibitors of cyclin-dependent kinase 2 (CDK2), a well-established therapeutic target in colorectal cancer. A comprehensive <em>in silico</em> approach was employed, including molecular docking, ADMET prediction, and drug-likeness evaluation. The ligands and their copper(I) complexes were docked against the CDK2 crystal structure (PDB ID: <span><span>2VTO</span><svg><path></path></svg></span>), and binding affinities were assessed. Before docking, all compounds were geometry optimized, and their electronic properties, such as total energy and HOMO/LUMO orbital distributions, were calculated to inform docking simulations. ProTox 3.0 predicted all compounds to be non-toxic across major endpoints, with inactivity probabilities ranging from 0.50 to 0.99. The results suggest that both the free ligands and their copper complexes exhibit favorable binding interactions with the CDK2 active site, supporting their potential as lead compounds for further development in colon cancer therapeutics. Molecular dynamics simulations using the selected OPLS-AA force field were performed to analyze RMSD, RMSF, and protein–ligand contacts for the best docking poses.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123087"},"PeriodicalIF":3.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074447","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 : 2026-01-22DOI: 10.1016/j.ica.2026.123086
Crystal M. Thompson , Elizabeth A. Tonsel-White , Gabriel M. Mercier , Garry S. Hanan , Alvin A. Holder , Mark A.W. Lawrence
Three Co(III) pincer complexes of the general formula [Co(L)I2(solv)]·(solv)n (solv = CH3CH2OH (n = 0) or H2O (n = 1) and L = bis-N-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (L1), N-(2,5-dimethoxyphenyl)-6-[(2,5-dimethoxyphenyl)carbamothioyl]pyridine-2-carboxamide (L2), and 6-(4,7-dimethoxy-2-benzothiazolyl)-N-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (L3); were prepared by oxidation of the corresponding Co(II) species using iodine in ethanol to give the Co(III) pincer complexes, 1–3. The Co(III) complexes were shown to be active electrocatalysts for hydrogen evolution reaction at an unmodified glassy carbon electrode in acetonitrile, with Faradaic efficiencies in the range 80–88%, and overpotentials between 490 and 670 mV with acetic acid as the proton source. Faradaic efficiencies ranging from 35 to 65% and overpotentials between 660 and 700 mV were obtained with p-toluene sulfonic acid monohydrate as the proton source. The potential for light-driven hydrogen production of the catalysts were evaluated under blue light (445 nm, 44 mW) under photocatalytic conditions using acetonitrile as solvent, triethanolamine as a sacrificial electron donor, tetrafluoroboric acid (HBF4, aqueous solution 48%) as a proton donor and ruthenium complex [RuII(bpy)3](PF6)2 as a photosensitizer (PS). Complex 1, which had a κ3-SNS coordination of the ligand, showed the best results, achieving a similar efficiency when compared to the [Co(dmgH)(dmgH2)Cl2] reference (within ca 90% of the TON and TOF) with a TON of up to 232 molH2.molcat−1 and a TOF of up to 13,880 mmolH2.molcat−1.min−1. Complexes 2 and 3 having κ3-ONS and κ3-SNN gave similar results, achieving TON ca. 130 molH2.molcat−1 and TOF ca. 11,000 mmolH2.molcat−1.min−1, respectively. Complex 1 was able to produce hydrogen over a longer period, suggesting that the κ3-SNS coordination mode improved the lifetime of the Co(III) and the transient species generated in the catalytic cycle.
{"title":"Co(III) pincer complexes bearing functionalized pyridyl benzothiazoles/(thio)amides for electro- and photo-catalytic hydrogen evolution reaction in acetonitrile","authors":"Crystal M. Thompson , Elizabeth A. Tonsel-White , Gabriel M. Mercier , Garry S. Hanan , Alvin A. Holder , Mark A.W. Lawrence","doi":"10.1016/j.ica.2026.123086","DOIUrl":"10.1016/j.ica.2026.123086","url":null,"abstract":"<div><div>Three Co(III) pincer complexes of the general formula [Co(<strong><em>L</em></strong>)I<sub>2</sub>(solv)]·(solv)<sub>n</sub> (solv = CH<sub>3</sub>CH<sub>2</sub>OH (<em>n</em> = 0) or H<sub>2</sub>O (<em>n</em> = 1) and <strong><em>L</em></strong> = bis-<em>N</em>-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (<strong><em>L</em></strong><sup><strong><em>1</em></strong></sup>), <em>N</em>-(2,5-dimethoxyphenyl)-6-[(2,5-dimethoxyphenyl)carbamothioyl]pyridine-2-carboxamide (<strong><em>L</em></strong><sup><strong><em>2</em></strong></sup>), and 6-(4,7-dimethoxy-2-benzothiazolyl)-<em>N</em>-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (<strong><em>L</em></strong><sup><strong>3</strong></sup>); were prepared by oxidation of the corresponding Co(II) species using iodine in ethanol to give the Co(III) pincer complexes, <strong>1</strong>–<strong>3</strong>. The Co(III) complexes were shown to be active electrocatalysts for hydrogen evolution reaction at an unmodified glassy carbon electrode in acetonitrile, with Faradaic efficiencies in the range 80–88%, and overpotentials between 490 and 670 mV with acetic acid as the proton source. Faradaic efficiencies ranging from 35 to 65% and overpotentials between 660 and 700 mV were obtained with <em>p</em>-toluene sulfonic acid monohydrate as the proton source. The potential for light-driven hydrogen production of the catalysts were evaluated under blue light (445 nm, 44 mW) under photocatalytic conditions using acetonitrile as solvent, triethanolamine as a sacrificial electron donor, tetrafluoroboric acid (HBF<sub>4</sub>, aqueous solution 48%) as a proton donor and ruthenium complex [Ru<sup>II</sup>(bpy)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub> as a photosensitizer (PS). Complex <strong>1,</strong> which had a κ<sup>3</sup>-SNS coordination of the ligand, showed the best results, achieving a similar efficiency when compared to the [Co(dmgH)(dmgH<sub>2</sub>)Cl<sub>2</sub>] reference (within ca 90% of the TON and TOF) with a TON of up to 232 mol<sub>H2</sub>.mol<sub>cat</sub><sup>−1</sup> and a TOF of up to 13,880 mmol<sub>H2</sub>.mol<sub>cat</sub><sup>−1</sup>.min<sup>−1</sup>. Complexes <strong>2</strong> and <strong>3</strong> having κ<sup>3</sup>-ONS and κ<sup>3</sup>-SNN gave similar results, achieving TON ca. 130 mol<sub>H2</sub>.mol<sub>cat</sub><sup>−1</sup> and TOF ca. 11,000 mmol<sub>H2</sub>.mol<sub>cat</sub><sup>−1</sup>.min<sup>−1</sup>, respectively. Complex <strong>1</strong> was able to produce hydrogen over a longer period, suggesting that the κ<sup>3</sup>-SNS coordination mode improved the lifetime of the Co(III) and the transient species generated in the catalytic cycle.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123086"},"PeriodicalIF":3.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074450","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 : 2026-01-21DOI: 10.1016/j.ica.2026.123089
Fen Wang , Yuhong Liu , Jianfeng Li, Chunming Cui
Rare-earth (RE) ate complexes, formed by the coordination of anionic ligands to neutral rare-earth complexes, have attracted increasing attention. The electronic and steric protection toward the central ions in rare-earth ate complexes significantly enhances their stability. Moreover, rare-earth alkyl and amide ate complexes have been shown to behave as promising catalysts, attributable not only to the unique electronic structures but also interatomic collaborations. This review focuses on structurally characterized rare-earth alkyl and amide ate complexes, emphasizing their synthesis, structural features, reactivity and catalytic applications.
{"title":"Rare-earth alkyl and amide ate complexes","authors":"Fen Wang , Yuhong Liu , Jianfeng Li, Chunming Cui","doi":"10.1016/j.ica.2026.123089","DOIUrl":"10.1016/j.ica.2026.123089","url":null,"abstract":"<div><div>Rare-earth (RE) ate complexes, formed by the coordination of anionic ligands to neutral rare-earth complexes, have attracted increasing attention. The electronic and steric protection toward the central ions in rare-earth ate complexes significantly enhances their stability. Moreover, rare-earth alkyl and amide ate complexes have been shown to behave as promising catalysts, attributable not only to the unique electronic structures but also interatomic collaborations. This review focuses on structurally characterized rare-earth alkyl and amide ate complexes, emphasizing their synthesis, structural features, reactivity and catalytic applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123089"},"PeriodicalIF":3.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074448","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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