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":"2026-06-01","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}
Complexes based on Group 14 element (Sn, Ge, Si) bis(3,6-di-tert-butylcatecholates) and various substituted pyridine derivatives were obtained in high yields. Single-crystal X-ray diffraction analysis revealed a distorted tetragonal bipyramid geometry at the coordination center. The synthesized compounds are brightly colored and exhibit low-intensity ligand-to-ligand charge transfer (LLCT) bands in the visible region of their electronic spectra. The UV–Vis spectroscopic data are in excellent agreement with quantum chemical calculations, which confirmed the LLCT mechanism for the electronic transitions. It was also demonstrated that the complexes decompose in the coordinating solvent tetrahydrofuran (THF), while the six-coordinate silicon complexes dissociate even in non-polar solvents such as toluene.
{"title":"Exploration of ligand-to-ligand charge transfer in complexes of group 14 elements with pyridine derivatives substituted by acceptor groups","authors":"A.V. Klimashevskaya , K.V. Arsenyeva , A.V. Maleeva , A.V. Cherkasov , I.A. Yakushev , A.V. Piskunov","doi":"10.1016/j.ica.2026.123124","DOIUrl":"10.1016/j.ica.2026.123124","url":null,"abstract":"<div><div>Complexes based on Group 14 element (Sn, Ge, Si) bis(3,6-di-tert-butylcatecholates) and various substituted pyridine derivatives were obtained in high yields. Single-crystal X-ray diffraction analysis revealed a distorted tetragonal bipyramid geometry at the coordination center. The synthesized compounds are brightly colored and exhibit low-intensity ligand-to-ligand charge transfer (LLCT) bands in the visible region of their electronic spectra. The UV–Vis spectroscopic data are in excellent agreement with quantum chemical calculations, which confirmed the LLCT mechanism for the electronic transitions. It was also demonstrated that the complexes decompose in the coordinating solvent tetrahydrofuran (THF), while the six-coordinate silicon complexes dissociate even in non-polar solvents such as toluene.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"596 ","pages":"Article 123124"},"PeriodicalIF":3.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146192459","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}
In this report, pyrazole-derived pincer-like azo-aromatic ligands L1 and L2 as well as their corresponding Cu(II) complexes [Cu(L)Cl2] (1a, and 1b), and Cu(I) complexes [Cu(L)Cl] (2a, and 2b) were synthesized and characterized. Ligands were redox non-innocent and their complexes exhibited very facile Cu(II)/Cu(I) redox event in anodic potential. The Cu(I) complexes subsequently showed multiple reductions. These redox events were thoroughly investigated by cyclic voltammetry, EPR, and DFT calculations. Redox active nature of the coordinated ligand in Cu(I) complexes 2a and 2b, enabled these to act as pre-catalysts for alcohol oxidation as well as alcohol oxidation-triggered synthesis of quinolines. Both primary including 2-amino aryl alcohol and secondary aromatic alcohols were oxidized efficiently. The catalytic protocol was also quite efficient for the synthesis of quinolines in 10-12 h directly from alcohols. Combinations of primary 2-aryl amino benzyl alcohol with secondary alcohol and secondary 2-aryl amino benzyl alcohol and secondary alcohols, were found to be very effective for the synthesis of quinolines.
{"title":"Redox non-innocent tridentate pyrazole-pyridine azo ligands and their Cu(I/II) complexes: Electrochemistry, alcohol oxidation catalysis, and alcohol oxidation triggered synthesis of quinolines","authors":"Ambika Devi , Bappaditya Goswami , Manas Khatua , Nisha Yadav , Robindo Chatterjee , Kamna , Vivekanand Jha , Subhas Samanta","doi":"10.1016/j.ica.2026.123122","DOIUrl":"10.1016/j.ica.2026.123122","url":null,"abstract":"<div><div>In this report, pyrazole-derived pincer-like azo-aromatic ligands <strong>L</strong><sup><strong>1</strong></sup> and <strong>L</strong><sup><strong>2</strong></sup> as well as their corresponding Cu(II) complexes [Cu(L)Cl<sub>2</sub>] (<strong>1a</strong>, and <strong>1b</strong>), and Cu(I) complexes [Cu(L)Cl] (<strong>2</strong><strong>a</strong>, and <strong>2b</strong>) were synthesized and characterized. Ligands were redox non-innocent and their complexes exhibited very facile Cu(II)/Cu(I) redox event in anodic potential. The Cu(I) complexes subsequently showed multiple reductions. These redox events were thoroughly investigated by cyclic voltammetry, EPR, and DFT calculations. Redox active nature of the coordinated ligand in Cu(I) complexes <strong>2</strong><strong>a</strong> and <strong>2b</strong>, enabled these to act as pre-catalysts for alcohol oxidation as well as alcohol oxidation-triggered synthesis of quinolines. Both primary including 2-amino aryl alcohol and secondary aromatic alcohols were oxidized efficiently. The catalytic protocol was also quite efficient for the synthesis of quinolines in 10-12 h directly from alcohols. Combinations of primary 2-aryl amino benzyl alcohol with secondary alcohol and secondary 2-aryl amino benzyl alcohol and secondary alcohols, were found to be very effective for the synthesis of quinolines.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123122"},"PeriodicalIF":3.2,"publicationDate":"2026-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191021","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 : 2026-05-24Epub 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":"2026-05-24","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 : 2026-05-24Epub 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":"2026-05-24","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}
[CoIIGdIII(L)(H2O)2(L´)2]ClO4 (1) [LH2 = 6,6′-((1E,1′E)-(propane-1,3-diylbis(azaneyl-ylidene))bis(methaneylylidene))bis(2-methoxyph-enol), L'H = o-vanillin (there are 2 and 1 acidic as well as ionizable phenolic OH protons in the former and latter ligands, respectively)] was synthesized and X-ray structurally characterized. It was crystallized in the monoclinic crystal system with P21/c space group. The geometry around Co(II) in 1 is octahedral whereas the 8 coordination surrounding Gd(III) in the molecule forms the geometry of snub diphenod. The Co(II) and Gd(III) centers in 1 are found to be antiferromagnetically coupled at low temperature range. Below 50 K possible spin canting results in softening the antiferromagnetic correlation in 1. More importantly, 1 exhibits field induced metamagnetic type transition where above 1.1 Tesla antialignment of Co(II) and Gd(III) spins is promoted suppressing the spin canting. Magnetostructural correlation of [ZnII2GdIII(L)2(H2O)Cl2]0.5ZnCl4.2H2O (2), which was synthesized previously, was done to make a comparative study with newly synthesizd 1. From variable temperature magnetic measurements, 2 appears expectedly as a free Gd(III) ion. The magnetic results of 1 are now correlated with the density functional theory calculations.
{"title":"Synthesis and structural characterization of [CoIIGdIII(L)(H2O)2(L´)2]ClO4 [LH2 = a Schiff base, L'H = o-vanillin], and magnetostructural correlations of [ZnII2GdIII(L)2(H2O)Cl2]0.5ZnCl4.2H2O and [CoIIGdIII(L)(H2O)2(L´)2]ClO41","authors":"Indrani Ray Chowdhury , Suraj Kumar Agrawalla , Sakshi Mehta , Chandra Shekhar Purohit , Md. Motin Seikh , Snehasis Banerjee , Rajarshi Ghosh","doi":"10.1016/j.ica.2026.123116","DOIUrl":"10.1016/j.ica.2026.123116","url":null,"abstract":"<div><div>[Co<sup>II</sup>Gd<sup>III</sup>(L)(H<sub>2</sub>O)<sub>2</sub>(L´)<sub>2</sub>]ClO<sub>4</sub> (<strong>1</strong>) [LH<sub>2</sub> = 6,6′-((1E,1′E)-(propane-1,3-diylbis(azaneyl-ylidene))bis(methaneylylidene))bis(2-methoxyph-enol), L'H = <em>o</em>-vanillin (there are 2 and 1 acidic as well as ionizable phenolic OH protons in the former and latter ligands, respectively)] was synthesized and X-ray structurally characterized. It was crystallized in the monoclinic crystal system with <em>P21/c</em> space group. The geometry around Co(II) in <strong>1</strong> is octahedral whereas the 8 coordination surrounding Gd(III) in the molecule forms the geometry of snub diphenod. The Co(II) and Gd(III) centers in <strong>1</strong> are found to be antiferromagnetically coupled at low temperature range. Below 50 K possible spin canting results in softening the antiferromagnetic correlation in <strong>1</strong>. More importantly, <strong>1</strong> exhibits field induced metamagnetic type transition where above 1.1 Tesla antialignment of Co(II) and Gd(III) spins is promoted suppressing the spin canting. Magnetostructural correlation of [Zn<sup>II</sup><sub>2</sub>Gd<sup>III</sup>(L)<sub>2</sub>(H<sub>2</sub>O)Cl<sub>2</sub>]0.5ZnCl<sub>4</sub>.2H<sub>2</sub>O (<strong>2</strong>), which was synthesized previously, was done to make a comparative study with newly synthesizd <strong>1</strong>. From variable temperature magnetic measurements, <strong>2</strong> appears expectedly as a free Gd(III) ion. The magnetic results of <strong>1</strong> are now correlated with the density functional theory calculations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123116"},"PeriodicalIF":3.2,"publicationDate":"2026-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191002","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 : 2026-05-24Epub 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":"2026-05-24","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 : 2026-05-24Epub Date: 2026-02-05DOI: 10.1016/j.ica.2026.123100
Arnab Patla , Basudeb Dutta , Aparup Paul , Ranga Subramanian , Saugata Konar
A new zinc(II) complex [Zn(L)(SCN)2] (1) of NNN donor Schiff base ligand L (where “L” = N-(4,6-dimethyl-pyrimidin-2-yl)-N′-pyridin-2-ylmethylene-hydrazine) is synthesized and characterized by elemental analysis and single crystal X-ray crystallography (XRD). Using the single-crystal X-ray diffraction technique, the structure of Complex 1 exhibits a distorted trigonal bipyramidal geometry. The crystal packing of 1 exhibits intermolecular S⋯H, π⋯π stacking interactions to generate a 1D network. These unique S⋯H interactions significantly affect the stability, arrangement, and prospective functional uses of the Complex. DFT calculations were used to determine the complex's electronic structure, using the pseudo-potential LANL2DZ for the zinc atom and the 6-31G+(d,p) basis set for the remaining atoms, at the B3LYP level. At this computational level, the optimized structure can accurately replicate the crystal structure. To comprehend the complex's reactivity properties, the molecule's electrostatic potential (MEP) and frontier molecular orbital analysis have been assessed. Natural bond orbital (NBO) analysis was used to illustrate the charge transfer between donor and acceptor sites. Additionally, fingerprint plots and Hirshfeld surface analysis are used to examine the complex's intermolecular interactions. Hirshfeld surface analysis, combined with two-dimensional fingerprint plots, provided a comparative visualization of the non-covalent interaction patterns in the synthesized complex.
{"title":"Crystallographic and quantum chemical methods to elucidate the structural and electronic characteristics of a Zn(II) complex","authors":"Arnab Patla , Basudeb Dutta , Aparup Paul , Ranga Subramanian , Saugata Konar","doi":"10.1016/j.ica.2026.123100","DOIUrl":"10.1016/j.ica.2026.123100","url":null,"abstract":"<div><div>A new zinc(II) complex [Zn(L)(SCN)<sub>2</sub>] (1) of NNN donor Schiff base ligand L (where “L” = N-(4,6-dimethyl-pyrimidin-2-yl)-N′-pyridin-2-ylmethylene-hydrazine) is synthesized and characterized by elemental analysis and single crystal X-ray crystallography (XRD). Using the single-crystal X-ray diffraction technique, the structure of Complex 1 exhibits a distorted trigonal bipyramidal geometry. The crystal packing of 1 exhibits intermolecular S⋯H, π⋯π stacking interactions to generate a 1D network. These unique S⋯H interactions significantly affect the stability, arrangement, and prospective functional uses of the Complex. DFT calculations were used to determine the complex's electronic structure, using the pseudo-potential LANL2DZ for the zinc atom and the 6-31G+(d,p) basis set for the remaining atoms, at the B3LYP level. At this computational level, the optimized structure can accurately replicate the crystal structure. To comprehend the complex's reactivity properties, the molecule's electrostatic potential (MEP) and frontier molecular orbital analysis have been assessed. Natural bond orbital (NBO) analysis was used to illustrate the charge transfer between donor and acceptor sites. Additionally, fingerprint plots and Hirshfeld surface analysis are used to examine the complex's intermolecular interactions. Hirshfeld surface analysis, combined with two-dimensional fingerprint plots, provided a comparative visualization of the non-covalent interaction patterns in the synthesized complex.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123100"},"PeriodicalIF":3.2,"publicationDate":"2026-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191020","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 : 2026-05-24Epub Date: 2026-02-06DOI: 10.1016/j.ica.2026.123117
Mmapule M. Phasha , Kwena D. Modibane , Kabelo E. Ramohlola , Reineck Mhlaba
Hydrogen (H₂) is a clean and sustainable energy carrier, offering high energy density and environmental benefits. However, efficient hydrogen production remains a challenge due to limitations in catalyst design, stability, and activity. Herein, we report the synthesis and evaluation of three calcium-based metal-organic frameworks (MOFs) Ca-BDC, Ca-BTC, and Ca-BTTC for photocatalytic and electrocatalytic hydrogen evolution. The structural and electronic properties of the MOFs were characterized using various analytical techniques, and their hydrogen evolution performance was assessed under visible light and electrochemical conditions. Ca-BDC exhibited the highest photocatalytic hydrogen production rate of 939.6 μ.mol /g/ h, attributed to its optimal bandgap and efficient electron transfer dynamics. In electrocatalysis, Ca-BTTC showed better stability and high turnover frequency (8.218 × 10−3 mol H₂ s−1 at 159.80 mV overpotential), while Ca-BTC demonstrated fast reaction kinetics. The reduced photocatalytic efficiency of Ca-BTC and Ca-BTTC is linked to their higher carboxylic acid content, which limits electron transport and increases bandgap. These findings show the potential of calcium-based MOFs as versatile catalysts for hydrogen production and highlight the importance of linker design and carboxylic acid optimization in enhancing catalytic activity.
{"title":"Calcium-based multi-carboxylate linker metal organic framework for photocatalytic and electrocatalytic hydrogen production","authors":"Mmapule M. Phasha , Kwena D. Modibane , Kabelo E. Ramohlola , Reineck Mhlaba","doi":"10.1016/j.ica.2026.123117","DOIUrl":"10.1016/j.ica.2026.123117","url":null,"abstract":"<div><div>Hydrogen (H₂) is a clean and sustainable energy carrier, offering high energy density and environmental benefits. However, efficient hydrogen production remains a challenge due to limitations in catalyst design, stability, and activity. Herein, we report the synthesis and evaluation of three calcium-based metal-organic frameworks (MOFs) Ca-BDC, Ca-BTC, and Ca-BTTC for photocatalytic and electrocatalytic hydrogen evolution. The structural and electronic properties of the MOFs were characterized using various analytical techniques, and their hydrogen evolution performance was assessed under visible light and electrochemical conditions. Ca-BDC exhibited the highest photocatalytic hydrogen production rate of 939.6 μ.mol /g/ h, attributed to its optimal bandgap and efficient electron transfer dynamics. In electrocatalysis, Ca-BTTC showed better stability and high turnover frequency (8.218 × 10<sup>−3</sup> mol H₂ s<sup>−1</sup> at 159.80 mV overpotential), while Ca-BTC demonstrated fast reaction kinetics. The reduced photocatalytic efficiency of Ca-BTC and Ca-BTTC is linked to their higher carboxylic acid content, which limits electron transport and increases bandgap. These findings show the potential of calcium-based MOFs as versatile catalysts for hydrogen production and highlight the importance of linker design and carboxylic acid optimization in enhancing catalytic activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123117"},"PeriodicalIF":3.2,"publicationDate":"2026-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191022","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 : 2026-05-24Epub Date: 2026-02-10DOI: 10.1016/j.ica.2026.123113
Pratik Mane , Pooja K. Bhoj , Arvind M.Yelpale , Vishal Burungale , Hyojung Bae , Anil Vithal Ghule , Sang Hyun Lee , Jun-Seok Ha
Despite being a well-known visible-light-responsive photoanode, n-type bismuth vanadate (BiVO4) suffers from intrinsic drawbacks such as limited carrier diffusion length, sluggish surface oxidation kinetics, poor electrical conductivity, and fast recombination of photogenerated charge carriers, all of which hinder its practical efficiency. To address these limitations, the rational design of a BiVO4-based heterostructure with efficient charge separation and enhanced surface redox activity is crucial for improving photoelectrochemical (PEC) water splitting and environmental remediation. Herein, we report a BiVO4@LDH heterostructured photoanode prepared via a facile two-step SILAR (Successive Ionic Layer Adsorption and Reaction) and electrodeposition approach. The uniform LDH (layered double hydroxide) coating on BiVO4 provides abundant surface hydroxyl groups, facilitates hole extraction, and improves interfacial charge transfer, leading to enhanced light utilization and accelerated surface redox reactions. PEC water splitting analysis revealed that, compared with the moderate photocurrent density of pristine BiVO4 (∼0.8 mA cm−2 at 1.23 V vs. RHE), the BiVO4@LDH photoanode exhibits a substantially higher photocurrent density of ∼1.6 mA cm−2. The photoanode retained its photocurrent over 15 h of continuous illumination, demonstrating excellent stability. Moreover, PEC dye degradation experiments showed that BiVO4@LDH achieved nearly 97% removal of methylene blue within 90 min, which is about 23% higher than the degradation efficiency of pristine BiVO4 (∼79%). This study emphasizes the cooperative role of the crystalline BiVO4 and the amorphous LDH interface, offering a sustainable and low-cost approach for developing efficient bifunctional photoanodes applicable to solar water splitting and wastewater treatment.
尽管是一种众所周知的可见光响应光阳极，但n型钒酸铋（BiVO4）存在载流子扩散长度有限、表面氧化动力学缓慢、导电性差、光生载流子重组速度快等固有缺陷，这些都阻碍了其实际效率。为了解决这些限制，合理设计具有高效电荷分离和增强表面氧化还原活性的bivo4基异质结构对于改善光电化学（PEC）水分解和环境修复至关重要。在此，我们报告了一个BiVO4@LDH异质结构光阳极通过简单的两步SILAR（连续离子层吸附和反应）和电沉积方法制备。BiVO4表面均匀的LDH（层状双氢氧化物）涂层提供了丰富的表面羟基，有利于空穴的提取，并改善了界面电荷转移，从而提高了光利用率，加速了表面氧化还原反应。PEC水分解分析显示，与原始BiVO4的中等光电流密度（在1.23 V vs. RHE时为~ 0.8 mA cm - 2）相比，BiVO4@LDH光阳极的光电流密度明显更高，为~ 1.6 mA cm - 2。光阳极在15小时的连续光照下保持其光电流，表现出优异的稳定性。此外，PEC染料降解实验表明，BiVO4@LDH在90分钟内对亚甲基蓝的去除率接近97%，比原始BiVO4的降解效率（~ 79%）高出约23%。本研究强调晶态BiVO4和非晶态LDH界面的协同作用，为开发适用于太阳能水分解和废水处理的高效双功能光阳极提供了可持续和低成本的途径。
{"title":"Maximizing BiVO4 photoanode efficacy via synergetic integration of amorphous NiFe-layered double hydroxide for bifunctional solar-driven water splitting and recalcitrant pollutant removal reactions","authors":"Pratik Mane , Pooja K. Bhoj , Arvind M.Yelpale , Vishal Burungale , Hyojung Bae , Anil Vithal Ghule , Sang Hyun Lee , Jun-Seok Ha","doi":"10.1016/j.ica.2026.123113","DOIUrl":"10.1016/j.ica.2026.123113","url":null,"abstract":"<div><div>Despite being a well-known visible-light-responsive photoanode, n-type bismuth vanadate (BiVO<sub>4</sub>) suffers from intrinsic drawbacks such as limited carrier diffusion length, sluggish surface oxidation kinetics, poor electrical conductivity, and fast recombination of photogenerated charge carriers, all of which hinder its practical efficiency. To address these limitations, the rational design of a BiVO<sub>4</sub>-based heterostructure with efficient charge separation and enhanced surface redox activity is crucial for improving photoelectrochemical (PEC) water splitting and environmental remediation. Herein, we report a BiVO<sub>4</sub>@LDH heterostructured photoanode prepared via a facile two-step SILAR (Successive Ionic Layer Adsorption and Reaction) and electrodeposition approach. The uniform LDH (layered double hydroxide) coating on BiVO<sub>4</sub> provides abundant surface hydroxyl groups, facilitates hole extraction, and improves interfacial charge transfer, leading to enhanced light utilization and accelerated surface redox reactions. PEC water splitting analysis revealed that, compared with the moderate photocurrent density of pristine BiVO<sub>4</sub> (∼0.8 mA cm<sup>−2</sup> at 1.23 V vs. RHE), the BiVO<sub>4</sub>@LDH photoanode exhibits a substantially higher photocurrent density of ∼1.6 mA cm<sup>−2</sup>. The photoanode retained its photocurrent over 15 h of continuous illumination, demonstrating excellent stability. Moreover, PEC dye degradation experiments showed that BiVO<sub>4</sub>@LDH achieved nearly 97% removal of methylene blue within 90 min, which is about 23% higher than the degradation efficiency of pristine BiVO<sub>4</sub> (∼79%). This study emphasizes the cooperative role of the crystalline BiVO<sub>4</sub> and the amorphous LDH interface, offering a sustainable and low-cost approach for developing efficient bifunctional photoanodes applicable to solar water splitting and wastewater treatment.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"595 ","pages":"Article 123113"},"PeriodicalIF":3.2,"publicationDate":"2026-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190997","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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