Pub Date : 2026-01-19DOI: 10.1016/j.ica.2026.123081
Josefredo R. Pliego Jr
The development of palladium-catalyzed nucleophilic aromatic fluorination is a noteworthy example of rational ligand design, with theoretical calculations playing a critical role throughout the process. This review presents the historical development of this catalysis, beginning with the first theoretical insights from Yandulov and Tran. In the sequence, the successful design of biaryl monophosphine ligands and experiments performed by Buchwald and coworkers are discussed. The last part is the recent new theoretical insights into the mechanism able to explain the formation of regioisomers, followed by in silico design of more powerful ligands. Along with the text, a close connection between theory and experiments is presented, providing a deep understanding of the mechanism.
{"title":"Mechanistic insights into palladium-catalyzed nucleophilic aromatic fluorination: From early discoveries to recent Design of new Ligands","authors":"Josefredo R. Pliego Jr","doi":"10.1016/j.ica.2026.123081","DOIUrl":"10.1016/j.ica.2026.123081","url":null,"abstract":"<div><div>The development of palladium-catalyzed nucleophilic aromatic fluorination is a noteworthy example of rational ligand design, with theoretical calculations playing a critical role throughout the process. This review presents the historical development of this catalysis, beginning with the first theoretical insights from Yandulov and Tran. In the sequence, the successful design of biaryl monophosphine ligands and experiments performed by Buchwald and coworkers are discussed. The last part is the recent new theoretical insights into the mechanism able to explain the formation of regioisomers, followed by in silico design of more powerful ligands. Along with the text, a close connection between theory and experiments is presented, providing a deep understanding of the mechanism.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123081"},"PeriodicalIF":3.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035665","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 : 2026-01-19DOI: 10.1016/j.ica.2026.123085
Manas Kumar Mahish , Dama Saren , Michael Bodensteiner , Ennio Zangrando , Subal Chandra Manna
Two dinuclear Ni(II) complexes, [Ni2(L1)2(N3)2(H2O)] (1) and [Ni2(L2)2(N3)1.675(NO3)0.325(H2O)] (2) (where HL1 = 2-[(2-ethylamino-ethylimino)-methyl]-6-methoxy-phenol; HL2 = 2-ethoxy-6-[(2-ethylamino-ethylimino)-methyl]-phenol) have been synthesized and structurally characterized by single crystal X-ray diffraction, UV–visible, IR, and mass spectroscopic studies. The diffraction study showed comparable structure for the two dinuclear complexes with the two metals exhibiting a distorted octahedral geometry but with a different chemical environment, built by a N4O2 set for Ni1 and N3O3 for Ni2. One ligand acts as tetradentate bridging the metals Ni1 and Ni2 with phenolate oxygen, while the other Schiff base is tridentate chelating Ni2 only. In addition, the metals are bridged by a μ1,1-azide, and Ni1 completes the coordination sphere though a terminal N azide and an aquo O atom. Complexes 1 and 2 form 1D supra-molecular network through H-bonding interactions. As complement of experimental investigations, density functional theory (DFT) calculations were performed using B3LYP method and LanL2MB basis set. The results show that complex 1 has a slightly higher HOMO-LUMO energy gap in comparison to complex 2. Calculated values of chemical potential and electronegativity are comparable for both the complexes. Complexes 1 and 2 show fluorescence emission with lifetimes of 0.23766 ns and 0.21073 ns, respectively.
{"title":"Phenoxido and azido bridged Schiff base coordinated dinuclear Ni(II) complexes: Syntheses, crystal structure and DFT calculation","authors":"Manas Kumar Mahish , Dama Saren , Michael Bodensteiner , Ennio Zangrando , Subal Chandra Manna","doi":"10.1016/j.ica.2026.123085","DOIUrl":"10.1016/j.ica.2026.123085","url":null,"abstract":"<div><div>Two dinuclear Ni(II) complexes, [Ni<sub>2</sub>(L<sup>1</sup>)<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)] (<strong>1</strong>) and [Ni<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(N<sub>3</sub>)<sub>1.675</sub>(NO<sub>3</sub>)<sub>0.325</sub>(H<sub>2</sub>O)] (<strong>2</strong>) (where HL<sup>1</sup> = 2-[(2-ethylamino-ethylimino)-methyl]-6-methoxy-phenol; HL<sup>2</sup> = 2-ethoxy-6-[(2-ethylamino-ethylimino)-methyl]-phenol) have been synthesized and structurally characterized by single crystal X-ray diffraction, UV–visible, IR, and mass spectroscopic studies. The diffraction study showed comparable structure for the two dinuclear complexes with the two metals exhibiting a distorted octahedral geometry but with a different chemical environment, built by a N<sub>4</sub>O<sub>2</sub> set for Ni1 and N<sub>3</sub>O<sub>3</sub> for Ni2. One ligand acts as tetradentate bridging the metals Ni1 and Ni2 with phenolate oxygen, while the other Schiff base is tridentate chelating Ni2 only. In addition, the metals are bridged by a μ1,1-azide, and Ni1 completes the coordination sphere though a terminal N azide and an aquo O atom. Complexes <strong>1</strong> and <strong>2</strong> form 1D supra-molecular network through H-bonding interactions. As complement of experimental investigations, density functional theory (DFT) calculations were performed using B3LYP method and LanL2MB basis set. The results show that complex <strong>1</strong> has a slightly higher HOMO-LUMO energy gap in comparison to complex <strong>2</strong>. Calculated values of chemical potential and electronegativity are comparable for both the complexes. Complexes <strong>1</strong> and <strong>2</strong> show fluorescence emission with lifetimes of 0.23766 ns and 0.21073 ns, respectively.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123085"},"PeriodicalIF":3.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074449","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 : 2026-01-18DOI: 10.1016/j.ica.2026.123079
Xiaoping Sun, Erik Ulvaeng, Kaylee Nott
The luminescence spectra of mixtures of the uranyl UO22+ (VI) ion (U) and each of the following aromatic molecules (Ar): diphenyl sulfide (Ph2S), benzene-1,4-diol (hydroquinone, Hq), anthracene (An), 4-nitrotoluene (NT), 1-chloro-4-nitrobenzene (CNB), and 2-naphthol (NaphOH), have been studied. For each of the Ar/U pairs, Ar was found to quench the luminescence of U; and U, on the other hand, was also found to quench the luminescence of Ar. The quenching efficiency of each Ar for the U* luminescence (IU0/IU) was determined to be dependent linearly on the Ar molarity: IU0/IU = 1 + Kq(Ar)[Ar] (Kq(Ar): quenching constant of Ar for the U* luminescence). The quenching efficiency of U for the Ar* luminescence (IAr0/IAr) was determined to be dependent linearly on the U molarity as well: IAr0/IAr = 1 + Kq(U)[U] (Kq(U): quenching constant of U for the Ar* luminescence). The quenching of the Ar* luminescence (Ar = Ph2S, Hq, and An) by U occurred via an irreversible charge-transfer from the excited state Ar* (LUMO) to the ground state U (LUMO) within an EDA complex [Ar*, U] giving an Ar radical (Ph2S+., Hq, or An+.) and UO2+ (V). The charge-transfer mechanism for luminescence quenching is supported by the UV–Vis and EPR spectroscopic studies. The luminescence spectra of the Ar/U mixtures (Ar = NT, CNB, and NaphOH) with variable Ar and U concentrations exhibited emissions of both Ar* and U*. Their spectral lines shared a common isosbestic point. This indicates reversible, quantitative electronic excitation energy transfer from Ar* (energy donor) to U (energy acceptor) leading to Ar and U*, giving rise to quenching of the Ar* luminescence by U, and the simultaneous backward transfer of electronic energy from U* to Ar (Ar* + U ⇄ Ar + U*). Kinetic analysis has been performed based on the reversible electronic energy transfer mechanism. All the results in this work can serve as the theoretical basis for development of high–efficiency UO22+–stimulated/sensitized phosphors.
{"title":"Luminescent spectroscopic studies of electronic excitation energy transfer between aromatic molecules and the uranyl UO22+ (VI) cation","authors":"Xiaoping Sun, Erik Ulvaeng, Kaylee Nott","doi":"10.1016/j.ica.2026.123079","DOIUrl":"10.1016/j.ica.2026.123079","url":null,"abstract":"<div><div>The luminescence spectra of mixtures of the uranyl UO<sub>2</sub><sup>2+</sup> (VI) ion (U) and each of the following aromatic molecules (Ar): diphenyl sulfide (Ph<sub>2</sub>S), benzene-1,4-diol (hydroquinone, Hq), anthracene (An), 4-nitrotoluene (NT), 1-chloro-4-nitrobenzene (CNB), and 2-naphthol (NaphOH), have been studied. For each of the Ar/U pairs, Ar was found to quench the luminescence of U; and U, on the other hand, was also found to quench the luminescence of Ar. The quenching efficiency of each Ar for the U* luminescence (I<sub>U</sub><sup>0</sup>/I<sub>U</sub>) was determined to be dependent linearly on the Ar molarity: I<sub>U</sub><sup>0</sup>/I<sub>U</sub> = 1 + K<sub>q(Ar)</sub>[Ar] (K<sub>q(Ar)</sub>: quenching constant of Ar for the U* luminescence). The quenching efficiency of U for the Ar* luminescence (I<sub>Ar</sub><sup>0</sup>/I<sub>Ar</sub>) was determined to be dependent linearly on the U molarity as well: I<sub>Ar</sub><sup>0</sup>/I<sub>Ar</sub> = 1 + K<sub>q(U)</sub>[U] (K<sub>q(U)</sub>: quenching constant of U for the Ar* luminescence). The quenching of the Ar* luminescence (Ar = Ph<sub>2</sub>S, Hq, and An) by U occurred via an irreversible charge-transfer from the excited state Ar* (LUMO) to the ground state U (LUMO) within an EDA complex [Ar*, U] giving an Ar radical (Ph<sub>2</sub>S<sup>+</sup><sup>.</sup>, Hq, or An<sup>+<strong>.</strong></sup>) and UO<sub>2</sub><sup>+</sup> (V). The charge-transfer mechanism for luminescence quenching is supported by the UV–Vis and EPR spectroscopic studies. The luminescence spectra of the Ar/U mixtures (Ar = NT, CNB, and NaphOH) with variable Ar and U concentrations exhibited emissions of both Ar* and U*. Their spectral lines shared a common isosbestic point. This indicates reversible, quantitative electronic excitation energy transfer from Ar* (energy donor) to U (energy acceptor) leading to Ar and U*, giving rise to quenching of the Ar* luminescence by U, and the simultaneous backward transfer of electronic energy from U* to Ar (Ar* + U ⇄ Ar + U*). Kinetic analysis has been performed based on the reversible electronic energy transfer mechanism. All the results in this work can serve as the theoretical basis for development of high–efficiency UO<sub>2</sub><sup>2+</sup>–stimulated/sensitized phosphors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123079"},"PeriodicalIF":3.2,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035666","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 : 2026-01-16DOI: 10.1016/j.ica.2026.123084
Candice Schlabach, Chibuzor Uwazie, Rui Zhang
Oxidation of iron(III) tetra-tert-butylphthalocyanine chloride [FeIII(tBu₄Pc)Cl] (1) with AgClO₃ in anaerobic CH₃CN rapidly afforded a new species (2), assigned as an iron(IV)-oxo complex, i.e., [FeIV(tBu₄Pc)O]. Its formation is rationalized by thermal homolysis of the OCl bond in the chlorate ligand, leading to a one-electron oxidation of the metal center. Species 2 was characterized by UV–vis spectroscopy and ESI-MS, including an 18O-isotope exchange experiment to confirm the formation of a transient Fe(IV)=O moiety. The oxidation reactivity of the resulting iron–oxo complex was evaluated with a range of organic substrates in CH₃CN, unless otherwise specified. Overall, the second-order rate constants determined under pseudo-first-order conditions revealed that 2 exhibits moderate and substrate-dependent reactivity with pronounced solvent effects, providing the first kinetic insight into iron–oxo chemistry on a phthalocyanine framework.
{"title":"Generation, characterization, and reactivity of a phthalocyanine iron–oxo complex","authors":"Candice Schlabach, Chibuzor Uwazie, Rui Zhang","doi":"10.1016/j.ica.2026.123084","DOIUrl":"10.1016/j.ica.2026.123084","url":null,"abstract":"<div><div>Oxidation of iron(III) tetra-<em>tert</em>-butylphthalocyanine chloride [Fe<sup>III</sup>(<sup><em>t</em></sup>Bu₄Pc)Cl] (<strong>1</strong>) with AgClO₃ in anaerobic CH₃CN rapidly afforded a new species (<strong>2</strong>), assigned as an iron(IV)-oxo complex, i.e., [Fe<sup>IV</sup>(<sup><em>t</em></sup>Bu₄Pc)O]. Its formation is rationalized by thermal homolysis of the O<img>Cl bond in the chlorate ligand, leading to a one-electron oxidation of the metal center. Species <strong>2</strong> was characterized by UV–vis spectroscopy and ESI-MS, including an <sup>18</sup>O-isotope exchange experiment to confirm the formation of a transient Fe(IV)=O moiety. The oxidation reactivity of the resulting iron–oxo complex was evaluated with a range of organic substrates in CH₃CN, unless otherwise specified. Overall, the second-order rate constants determined under pseudo-first-order conditions revealed that <strong>2</strong> exhibits moderate and substrate-dependent reactivity with pronounced solvent effects, providing the first kinetic insight into iron–oxo chemistry on a phthalocyanine framework.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123084"},"PeriodicalIF":3.2,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035664","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 : 2026-01-14DOI: 10.1016/j.ica.2026.123083
Seema Nagarajan, Ankit Kumar Srivastava, Samudranil Pal
Reaction of Co(ClO4)2·6H2O, N,N′-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (H2L, where 2 Hs stand for the two phenolic protons) and NEt3 in 1:1:2 mol ratio in acetonitrile under aerobic conditions at 298 K produced [Co2(μ2-OH)2(L)2] (1), [Co(L′)2]ClO4 (2), and [Co3(μ3-O)(μ2-OH)(μ2-L)2(L′)]ClO4·2H2O (3·2H2O) (HL′ = N-salicylidene-2-methyl-2-(2H-1,3-benzoxazine-2-yl)propylamine, where H denotes the phenolic proton). All three complexes were characterized by ESI-MS, IR and UV–Vis spectroscopic, and X-ray crystallographic measurements. The physical characteristics and the X-ray structures are consistent with the molecular formulas and +3 oxidation state of the metal centers in all three complexes. The structures revealed that one of the two 2-((methyleneimino)methyl)phenol (–CH2N=CHC6H4OH) arms of H2L is changed to 2H-1,3-benzoxazine, leading to the formation of HL′. The ON2O-donor (L)2− occupies one axial and three meridional positions in both 1 and 3·2H2O, while the transformed ligand (L′)− acts as a facially coordinating N2O-donor in both 2 and 3·2H2O. The metal centers are in distorted octahedral N2O4 coordination spheres in 1 and 3·2H2O. In contrast, the metal center has a distorted octahedral N4O2 coordination environment in 2. Based on EPR and ESI-MS studies, a mechanism for the observed ligand transformation via metal-assisted alkyl C–H activation followed by C–O bond formation involving a radical intermediate has been proposed.
{"title":"Mono-, di-, and trinuclear cobalt(III) complexes with a H2salpn derivative: metal-assisted ligand transformation leading to the unusual formation of 2H-1,3-benzoxazine ring","authors":"Seema Nagarajan, Ankit Kumar Srivastava, Samudranil Pal","doi":"10.1016/j.ica.2026.123083","DOIUrl":"10.1016/j.ica.2026.123083","url":null,"abstract":"<div><div>Reaction of Co(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O, <em>N</em>,<em>N′</em>-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (H<sub>2</sub>L, where 2 Hs stand for the two phenolic protons) and NEt<sub>3</sub> in 1:1:2 mol ratio in acetonitrile under aerobic conditions at 298 K produced [Co<sub>2</sub>(μ<sub>2</sub>-OH)<sub>2</sub>(L)<sub>2</sub>] (<strong>1</strong>), [Co(L′)<sub>2</sub>]ClO<sub>4</sub> (<strong>2</strong>), and [Co<sub>3</sub>(μ<sub>3</sub>-O)(μ<sub>2</sub>-OH)(μ<sub>2</sub>-L)<sub>2</sub>(L′)]ClO<sub>4</sub>·2H<sub>2</sub>O (<strong>3</strong>·2H<sub>2</sub>O) (HL′ = <em>N</em>-salicylidene-2-methyl-2-(2H-1,3-benzoxazine-2-yl)propylamine, where H denotes the phenolic proton). All three complexes were characterized by ESI-MS, IR and UV–Vis spectroscopic, and X-ray crystallographic measurements. The physical characteristics and the X-ray structures are consistent with the molecular formulas and +3 oxidation state of the metal centers in all three complexes. The structures revealed that one of the two 2-((methyleneimino)methyl)phenol (–CH<sub>2</sub>N=CHC<sub>6</sub>H<sub>4</sub>OH) arms of H<sub>2</sub>L is changed to 2H-1,3-benzoxazine, leading to the formation of HL′. The ON<sub>2</sub>O-donor (L)<sup>2−</sup> occupies one axial and three meridional positions in both <strong>1</strong> and <strong>3</strong>·2H<sub>2</sub>O, while the transformed ligand (L′)<sup>−</sup> acts as a facially coordinating N<sub>2</sub>O-donor in both <strong>2</strong> and <strong>3</strong>·2H<sub>2</sub>O. The metal centers are in distorted octahedral N<sub>2</sub>O<sub>4</sub> coordination spheres in <strong>1</strong> and <strong>3</strong>·2H<sub>2</sub>O. In contrast, the metal center has a distorted octahedral N<sub>4</sub>O<sub>2</sub> coordination environment in <strong>2</strong>. Based on EPR and ESI-MS studies, a mechanism for the observed ligand transformation via metal-assisted alkyl C–H activation followed by C–O bond formation involving a radical intermediate has been proposed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123083"},"PeriodicalIF":3.2,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035663","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 : 2026-01-14DOI: 10.1016/j.ica.2026.123080
Sondos A.J. Almahmoud , Md. Mohon Shek , Soad S. Alzahrani , Md. Shakil Hossen , Wisnu Arfian A. Sudjarwo , Asma Rshood Alshraim , A.F.M. Motiur Rahman , Abdullah Alodhayb , Shofiur Rahman , Paris E. Georghiou
Mercury contamination in the natural environment and from industrial products and their by-products poses well-documented public health concerns due to its toxicity, persistence, and bioaccumulation. The present study reports on the synthesis and properties of the symmetrical bis-Schiff base ligand, (1E,1E′)-N,N′-(1,4-phenylene)bis(1-(pyridin-2-yl)methanimine) (“NPIL”), which exhibits a rapid and distinct colorless to dark yellow colorimetric change upon complexation with Hg2+ ions in DMSO media, enabling naked-eye detection. UV–Vis titration in DMSO revealed a strong association constant (Ka = 4.8 × 103 M−1) and a low detection limit (LOD) of 0.027 μM and a quantification limit (LOQ) of 23 μM. The LOD is substantially below Health Canada's recommended value of 2.48 μM. The coordination of Hg2+ via the ligand's imine and pyridine nitrogen atoms, as ascertained from 1H NMR titration experiments in DMSO‑d6 suggested 2:1, 2:2, and 4:4 metal-to-ligand stoichiometries. Density functional theory (DFT) calculations were performed for several conformations of the host ligand NPIL and its complexes with HgCl₂ in DMSO. The binding interaction energies showed that of four possible “A-D" conformations of NPIL examined, a 2:1 HgCl2 complex with the All-cisD conformation (−113.30 kJ·mol−1) is more stable than the 2:1 HgCl2 complex with the Cis-trans-cisC conformation (−111.50 kJ·mol−1) due to strong ligand-to-metal charge transfer and stabilizing noncovalent interactions. The combination of high sensitivity, selective optical response, and its simple synthesis makes NPIL a suitable candidate as a cost-effective UV–vis probe for mercury ion detection.
{"title":"Experimental and DFT study of the bis-Schiff base N,N′-pyridyl-imine ligand as a probe for Hg2+ in DMSO solvent","authors":"Sondos A.J. Almahmoud , Md. Mohon Shek , Soad S. Alzahrani , Md. Shakil Hossen , Wisnu Arfian A. Sudjarwo , Asma Rshood Alshraim , A.F.M. Motiur Rahman , Abdullah Alodhayb , Shofiur Rahman , Paris E. Georghiou","doi":"10.1016/j.ica.2026.123080","DOIUrl":"10.1016/j.ica.2026.123080","url":null,"abstract":"<div><div>Mercury contamination in the natural environment and from industrial products and their by-products poses well-documented public health concerns due to its toxicity, persistence, and bioaccumulation. The present study reports on the synthesis and properties of the symmetrical bis-Schiff base ligand, (<em>1E,1E′</em>)-<em>N,N′</em>-(1,4-phenylene)bis(1-(pyridin-2-yl)methanimine) (“<strong>NPIL”</strong>), which exhibits a rapid and distinct colorless to dark yellow colorimetric change upon complexation with Hg<sup>2+</sup> ions in DMSO media, enabling naked-eye detection. UV–Vis titration in DMSO revealed a strong association constant (<em>K</em>a = 4.8 × 10<sup>3</sup> M<sup>−1</sup>) and a low detection limit (LOD) of 0.027 μM and a quantification limit (LOQ) of 23 μM. The LOD is substantially below Health Canada's recommended value of 2.48 μM. The coordination of Hg<sup>2+</sup> via the ligand's imine and pyridine nitrogen atoms, as ascertained from <sup>1</sup>H NMR titration experiments in DMSO‑<em>d</em><sub>6</sub> suggested 2:1, 2:2, and 4:4 metal-to-ligand stoichiometries. Density functional theory (DFT) calculations were performed for several conformations of the host ligand <strong>NPIL</strong> and its complexes with HgCl₂ in DMSO. The binding interaction energies showed that of four possible “<strong><em>A</em></strong>-<strong><em>D</em></strong>\" conformations of <strong>NPIL</strong> examined, a 2:1 HgCl<sub>2</sub> complex with the <em>All-cis</em> <strong>D</strong> conformation (−113.30 kJ·mol<sup>−1</sup>) is more stable than the 2:1 HgCl<sub>2</sub> complex with the <em>Cis-trans-cis</em> <strong>C</strong> conformation (−111.50 kJ·mol<sup>−1</sup>) due to strong ligand-to-metal charge transfer and stabilizing noncovalent interactions. The combination of high sensitivity, selective optical response, and its simple synthesis makes <strong>NPIL</strong> a suitable candidate as a cost-effective UV–vis probe for mercury ion detection.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123080"},"PeriodicalIF":3.2,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035765","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}
Hydroboration of alkenes offers an atom-economical method for producing alkylboronates, which are valuable intermediates in organic synthesis. We report the development of a single-site iron(II) hydride species supported by bipyridine-functionalized UiO metal-organic frameworks (bpy-UiO-FeH2), which serves as a highly active heterogeneous catalyst for selective anti-Markovnikov hydroboration of alkenes. The catalyst yields anti-Markovnikov boronate ester products with up to 94% selectivity at 60 °C and exhibits broad substrate compatibility, accommodating alkenes with diverse substitution patterns and functional groups. In comparison to its homogeneous counterpart (bipyridine–Fe), bpy-UiO-FeH2 demonstrates superior activity, enhanced selectivity, and excellent recyclability due to the active site isolation of the mononuclear bpy–FeH2 species within the MOF scaffold, which suppresses intermolecular decomposition pathways. Detailed mechanistic studies on styrene hydroboration, supported by control experiments, spectroscopic analyses, and computational investigations, revealed key insights into the catalytic pathway. This study underscores the potential of MOF-supported earth-abundant metal catalysts for environmentally friendly organic transformations.
{"title":"Regioselective hydroboration of alkenes by metal-organic framework confined mononuclear bipyridyl–iron hydride catalyst","authors":"Aditya Kumar , Rahul Kalita , Poorvi Gupta, Bharti Rana, Manav Chauhan, Kuntal Manna","doi":"10.1016/j.ica.2026.123082","DOIUrl":"10.1016/j.ica.2026.123082","url":null,"abstract":"<div><div>Hydroboration of alkenes offers an atom-economical method for producing alkylboronates, which are valuable intermediates in organic synthesis. We report the development of a single-site iron(II) hydride species supported by bipyridine-functionalized UiO metal-organic frameworks (bpy-UiO-FeH<sub>2</sub>), which serves as a highly active heterogeneous catalyst for selective anti-Markovnikov hydroboration of alkenes. The catalyst yields anti-Markovnikov boronate ester products with up to 94% selectivity at 60 °C and exhibits broad substrate compatibility, accommodating alkenes with diverse substitution patterns and functional groups. In comparison to its homogeneous counterpart (bipyridine–Fe), bpy-UiO-FeH<sub>2</sub> demonstrates superior activity, enhanced selectivity, and excellent recyclability due to the active site isolation of the mononuclear bpy–FeH<sub>2</sub> species within the MOF scaffold, which suppresses intermolecular decomposition pathways. Detailed mechanistic studies on styrene hydroboration, supported by control experiments, spectroscopic analyses, and computational investigations, revealed key insights into the catalytic pathway. This study underscores the potential of MOF-supported earth-abundant metal catalysts for environmentally friendly organic transformations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123082"},"PeriodicalIF":3.2,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035764","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 : 2026-01-10DOI: 10.1016/j.ica.2026.123076
Debashree Das , Sampurna Bhattacharya , Shalmali Basu , Saptydeep Das , Ujjal Das , David J. Morgan , Kamalika Sen
A novel folic acid-conjugated composite nanoparticle containing Cu on TeO2 (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 103 cells/mL. XPS analyses confirmed the transformation of Cu2+ to Cu0, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC50 of 15 μg/mL. A moderate DNA binding affinity (Kd = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.
{"title":"Theranostics of folic acid conjugated cu on Te nanocomposite: Fluorescence sensing, imaging and selective cytotoxicity towards HeLa cells1","authors":"Debashree Das , Sampurna Bhattacharya , Shalmali Basu , Saptydeep Das , Ujjal Das , David J. Morgan , Kamalika Sen","doi":"10.1016/j.ica.2026.123076","DOIUrl":"10.1016/j.ica.2026.123076","url":null,"abstract":"<div><div>A novel folic acid-conjugated composite nanoparticle containing Cu on TeO<sub>2</sub> (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 10<sup>3</sup> cells/mL. XPS analyses confirmed the transformation of Cu<sup>2+</sup> to Cu<sup>0</sup>, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC<sub>50</sub> of 15 μg/mL. A moderate DNA binding affinity (K<sub>d</sub> = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123076"},"PeriodicalIF":3.2,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975669","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}
Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion via the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound via (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.
{"title":"Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects","authors":"Amir Karim , Rahime Eshaghi Malekshah , Najeeb Ullah , Sodio C.N. Hsu","doi":"10.1016/j.ica.2026.123077","DOIUrl":"10.1016/j.ica.2026.123077","url":null,"abstract":"<div><div>Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion <em>via</em> the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound <em>via</em> (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123077"},"PeriodicalIF":3.2,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035754","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 : 2026-01-08DOI: 10.1016/j.ica.2026.123067
Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang
Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM−1 cm−2. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.
{"title":"Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice","authors":"Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang","doi":"10.1016/j.ica.2026.123067","DOIUrl":"10.1016/j.ica.2026.123067","url":null,"abstract":"<div><div>Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM<sup>−1</sup> cm<sup>−2</sup>. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123067"},"PeriodicalIF":3.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950249","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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