Pub Date : 2026-01-03DOI: 10.1016/j.ica.2026.123063
Medhavi D. Khatavkar , Rishukumar Panday , Mayank U. Singh , Sreekumar Kurungot , Avinash S. Kumbhar
A dinuclear complex of copper(II) and bipyridine glycoluril (BPG) ligand is synthesized, characterized, and structurally examined by single-crystal X-ray diffraction. The complex [Cu2(BPG)2(NO3)2(H2O)4](NO3)2ꞏ5H2O (complex (1)) further forms a supramolecular network sustained by H-bonds between NH/C=O of BPG, coordinated/free water molecules, and nitrate anions. The complex exhibits a proton conductivity of 5.99 × 10−3 Sꞏcm−1 at 90 °C and 95 % relative humidity (RH) with activation energy value Ea 0.35 eV, suggesting the Grötthuss proton transport mechanism. This value is consistent with those reported for proton-conducting systems in which coordinated water molecules play a critical role in facilitating efficient proton hopping across hydrogen-bonded networks.
{"title":"Proton conductivity in a copper(II) bipyridine glycoluril complex: The synergistic role of coordinated water and hydrogen-bonded networks.","authors":"Medhavi D. Khatavkar , Rishukumar Panday , Mayank U. Singh , Sreekumar Kurungot , Avinash S. Kumbhar","doi":"10.1016/j.ica.2026.123063","DOIUrl":"10.1016/j.ica.2026.123063","url":null,"abstract":"<div><div>A dinuclear complex of copper(II) and bipyridine glycoluril (BPG) ligand is synthesized, characterized, and structurally examined by single-crystal X-ray diffraction. The complex [Cu<sub>2</sub>(BPG)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>](NO<sub>3</sub>)<sub>2</sub>ꞏ5H<sub>2</sub>O (complex (<strong>1</strong>)) further forms a supramolecular network sustained by H-bonds between NH/C=O of BPG, coordinated/free water molecules, and nitrate anions. The complex exhibits a proton conductivity of 5.99 × 10<sup>−3</sup> Sꞏcm<sup>−1</sup> at 90 °C and 95 % relative humidity (RH) with activation energy value E<sub>a</sub> 0.35 eV, suggesting the Grötthuss proton transport mechanism. This value is consistent with those reported for proton-conducting systems in which coordinated water molecules play a critical role in facilitating efficient proton hopping across hydrogen-bonded networks.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123063"},"PeriodicalIF":3.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976029","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 : 2026-01-02DOI: 10.1016/j.ica.2026.123062
Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün
A series of morpholine(Morp.)-liganded palladium(II) complexes (1a–c) and triphenylphosphine(PPh3)-liganded palladium(II) complexes (2a–c) bearing 4-fluorobenzyl substituted N-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh3 by ligand exchange method. The new complexes were fully characterized using 1H NMR, 13C NMR, 19F NMR, 31P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes 1a and 2b. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex 1a, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex 1b.
{"title":"New morpholine or triphenylphosphine-liganded palladium(II) N-heterocyclic carbene complexes: Synthesis, characterization, crystal structure, and anticancer activity","authors":"Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün","doi":"10.1016/j.ica.2026.123062","DOIUrl":"10.1016/j.ica.2026.123062","url":null,"abstract":"<div><div>A series of morpholine(Morp.)-liganded palladium(II) complexes (<strong>1a–c</strong>) and triphenylphosphine(PPh<sub>3</sub>)-liganded palladium(II) complexes (<strong>2a–c</strong>) bearing 4-fluorobenzyl substituted <em>N</em>-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh<sub>3</sub> by ligand exchange method. The new complexes were fully characterized using <sup>1</sup>H NMR, <sup>13</sup>C NMR, <sup>19</sup>F NMR, <sup>31</sup>P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes <strong>1a</strong> and <strong>2b</strong>. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex <strong>1a</strong>, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex <strong>1b</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123062"},"PeriodicalIF":3.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939948","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 : 2025-12-30DOI: 10.1016/j.ica.2025.123058
Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal
The diborane(4) (B2H4) and diborene(2) (B2H2) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the BB bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B2H4 and B2H2 species remains unexplored. Thus the bonding interactions between B2H4/B2H2 and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)2}2{B2H4}] (1) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)2}2B2H2W(CO)4] (2), [{CpW(CO)2}2B2H2Mo(CO)4] (3) and [{CpW(CO)2}2B2H2W(CO)4] (4) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in 1–4 are primarily governed by electrostatic forces (ΔEelec) with notable covalent contributions (ΔEorb). Although 2–4 is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds 2-3 show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in 4 [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound 1. The B2H2 metal-carbonyl bonding interaction is much stronger in 2–3 (∼80–90 kcal/mol higher) compared to 4. Orbital analysis indicates predominant σ-donation from B2H4/B2H2, and in 4, additional π-backdonation from the metal centers strengthens the BB bond.
{"title":"Nature of bonding between B2H4/B2H2 with Homo-/hetero- Di/tri-nuclear-metal-carbonyls","authors":"Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal","doi":"10.1016/j.ica.2025.123058","DOIUrl":"10.1016/j.ica.2025.123058","url":null,"abstract":"<div><div>The diborane(4) (B<sub>2</sub>H<sub>4</sub>) and diborene(2) (B<sub>2</sub>H<sub>2</sub>) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the B<img>B bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B<sub>2</sub>H<sub>4</sub> and B<sub>2</sub>H<sub>2</sub> species remains unexplored. Thus the bonding interactions between B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub> and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)<sub>2</sub>}<sub>2</sub>{B<sub>2</sub>H<sub>4</sub>}] (<strong>1</strong>) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>2</strong>), [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>Mo(CO)<sub>4</sub>] (<strong>3</strong>) and [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>4</strong>) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in <strong>1–4</strong> are primarily governed by electrostatic forces (Δ<em>E</em><sub>elec</sub>) with notable covalent contributions (Δ<em>E</em><sub>orb</sub>). Although <strong>2–4</strong> is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds <strong>2-3</strong> show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in <strong>4</strong> [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound <strong>1</strong>. The B<sub>2</sub>H<sub>2</sub> metal-carbonyl bonding interaction is much stronger in <strong>2</strong>–<strong>3</strong> (∼80–90 kcal/mol higher) compared to <strong>4</strong>. Orbital analysis indicates predominant σ-donation from B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub>, and in <strong>4</strong>, additional π-backdonation from the metal centers strengthens the B<img>B bond.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123058"},"PeriodicalIF":3.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939884","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 addition of calcium phosphate to lead silicate glasses K2O-PbO-SiO2 results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K2O-PbO-SiO2 glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.
{"title":"The phase separation in K2O-PbO-CaO-P2O5-SiO2 glass doped by gold and Eu3+ ions","authors":"Ilya Salakheev , Andrey Drozdov , Maksim Andreev , Claudio Pettinari","doi":"10.1016/j.ica.2025.123048","DOIUrl":"10.1016/j.ica.2025.123048","url":null,"abstract":"<div><div>The addition of calcium phosphate to lead silicate glasses K<sub>2</sub>O-PbO-SiO<sub>2</sub> results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K<sub>2</sub>O-PbO-SiO<sub>2</sub> glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123048"},"PeriodicalIF":3.2,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939885","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 : 2025-12-29DOI: 10.1016/j.ica.2025.123049
Feng-Li Chen , Ao-Na Sun , Xing-Yi Yu , Jiong Yang , Dong Shao
A nickel(II) hydrogen-bonded-organdisulfonate framework, [Ni(bpy)(H2O)4][bpds]·4H2O (NiHOF-101, bpy = 2,2’-Bipyridyl, H2bpds = 4,4’-Biphenyldisulfonic acid) was synthesized and characterized in terms of structure, magnetic, and proton conduction properties. Crystallographic analysis reveals a three-dimensional hydrogen-bonded network stabilized by charge-assisted OH⋯O interactions involving coordinated and lattice water molecules with sulfonate groups. Magnetic measurements indicate the high-spin state of the Ni2+ ion showing easy-axis magnetic anisotropy with the D value being −13.7 cm−1. However, the NiHOF displayed non-single-ion magnet behavior. Ac impedance spectroscopy indicated this NiHOF is a superionic proton conductor with the highest measured conductivity being 3.24 × 10−3 S cm−1 at 60 °C under 95 % relative humility through a Grotthuss mechanism. Structural analysis reveals abundant coordinated and lattice water molecules interacting with well-oriented sulfonate groups should be responsible for the highly efficient proton transport. This work highlights a potential strategy for constructing supramolecular solid state proton conductors (SSPCs) through mixed bipyridyl-organodisulfonic ligands.
{"title":"A proton-conducting nickel(II) hydrogen-bonded organic framework assembled from mixed bipyridyl-organodisulfonic ligands","authors":"Feng-Li Chen , Ao-Na Sun , Xing-Yi Yu , Jiong Yang , Dong Shao","doi":"10.1016/j.ica.2025.123049","DOIUrl":"10.1016/j.ica.2025.123049","url":null,"abstract":"<div><div>A nickel(II) hydrogen-bonded-organdisulfonate framework, [Ni(bpy)(H<sub>2</sub>O)<sub>4</sub>][bpds]·4H<sub>2</sub>O (<strong>NiHOF-101</strong>, <strong>bpy</strong> = 2,2’-Bipyridyl, <strong>H</strong><sub><strong>2</strong></sub><strong>bpds</strong> = 4,4’-Biphenyldisulfonic acid) was synthesized and characterized in terms of structure, magnetic, and proton conduction properties. Crystallographic analysis reveals a three-dimensional hydrogen-bonded network stabilized by charge-assisted O<img>H⋯O interactions involving coordinated and lattice water molecules with sulfonate groups. Magnetic measurements indicate the high-spin state of the Ni<sup>2+</sup> ion showing easy-axis magnetic anisotropy with the D value being −13.7 cm<sup>−1</sup>. However, the NiHOF displayed non-single-ion magnet behavior. Ac impedance spectroscopy indicated this NiHOF is a superionic proton conductor with the highest measured conductivity being 3.24 × 10<sup>−3</sup> S cm<sup>−1</sup> at 60 °C under 95 % relative humility through a Grotthuss mechanism. Structural analysis reveals abundant coordinated and lattice water molecules interacting with well-oriented sulfonate groups should be responsible for the highly efficient proton transport. This work highlights a potential strategy for constructing supramolecular solid state proton conductors (SSPCs) through mixed bipyridyl-organodisulfonic ligands.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123049"},"PeriodicalIF":3.2,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882486","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 : 2025-12-28DOI: 10.1016/j.ica.2025.123047
Islam M. Elnabky , Mohamed M. Aboelnga , Hoda M. El-Gharabawy , Shadia A. Elsayed , Ahmed M. El-Hendawy
Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H2L) with composition [M(L)(X)] (M = Ni or Pd; X = H2O for Ni1, Pd1, or imidazole for Ni2, Pd2) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, 1H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand via deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (Ni2 and Pd1,2) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 104 M−1). Molecular docking further confirmed stable interactions with both biomolecules. The in vitro cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the Pd2 complex exhibited the most potent activity, especially against MDA-MB-231 (IC50 = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The Ni1 and Ni2 complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly Pd2, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.
{"title":"Dehydroacetic acid benzoyl hydrazone complexes of Ni(II) and Pd(II): Synthesis, characterization, computational studies, biomolecular interaction, and dual anticancer–antimicrobial activities","authors":"Islam M. Elnabky , Mohamed M. Aboelnga , Hoda M. El-Gharabawy , Shadia A. Elsayed , Ahmed M. El-Hendawy","doi":"10.1016/j.ica.2025.123047","DOIUrl":"10.1016/j.ica.2025.123047","url":null,"abstract":"<div><div>Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H<sub>2</sub>L) with composition [M(L)(X)] (M = Ni or Pd; X = H<sub>2</sub>O for <strong>Ni1</strong>, <strong>Pd1,</strong> or imidazole for <strong>Ni2</strong>, <strong>Pd2</strong>) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, <sup>1</sup>H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand <em>via</em> deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (<strong>Ni2</strong> and <strong>Pd1,2</strong>) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 10<sup>4</sup> M<sup>−1</sup>). Molecular docking further confirmed stable interactions with both biomolecules. The <em>in vitro</em> cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the <strong>Pd2</strong> complex exhibited the most potent activity, especially against MDA-MB-231 (IC<sub>50</sub> = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The <strong>Ni1</strong> and <strong>Ni2</strong> complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly <strong>Pd2</strong>, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123047"},"PeriodicalIF":3.2,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882484","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 : 2025-12-27DOI: 10.1016/j.ica.2025.123044
Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang
Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO3)(H2O)]n (1) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm2(OH-bdc)2(H2O)10]·OH-bdc·H2O}n (2) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound 1 features a three dimensional (3D) pillared layer network containing [Tm2(NO3)2]4+ units and 2,5-dtc2− ligands. Compound 2 exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm2(bdc)2(H2O)10]2+ to uncoordinated OH-bdc2− ligands via π···π stacking interactions. The striking feature of compounds 1 and 2 is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds 1 and 2 display antiferromagnetic coupling in the solid state at room temperature.
{"title":"Near-infrared (NIR) luminescence of two Tm(III)-based dicarboxylate coordination polymers","authors":"Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang","doi":"10.1016/j.ica.2025.123044","DOIUrl":"10.1016/j.ica.2025.123044","url":null,"abstract":"<div><div>Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO<sub>3</sub>)(H<sub>2</sub>O)]<sub><em>n</em></sub> (<strong>1</strong>) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm<sub>2</sub>(OH-bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]·OH-bdc·H<sub>2</sub>O}<sub><em>n</em></sub> (<strong>2</strong>) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound <strong>1</strong> features a three dimensional (3D) pillared layer network containing [Tm<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>]<sup>4+</sup> units and 2,5-dtc<sup>2−</sup> ligands. Compound <strong>2</strong> exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm<sub>2</sub>(bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]<sup>2+</sup> to uncoordinated OH-bdc<sup>2−</sup> ligands via <em>π···π</em> stacking interactions. The striking feature of compounds <strong>1</strong> and <strong>2</strong> is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds <strong>1</strong> and <strong>2</strong> display antiferromagnetic coupling in the solid state at room temperature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123044"},"PeriodicalIF":3.2,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939886","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 : 2025-12-27DOI: 10.1016/j.ica.2025.123046
Nawishta Jabeen , Ali Yaqoob , Ahmad Hussain , Aseel Smerat , Mohamed A. Nassan , Nidhal Ben Khedher
DFT based simulations have been performed to investigate the structural, optoelectronics, thermodynamics and mechanical properties of double anionic structured (alkaline selenite oxo-fluoro) compounds (XSeO3F where X = Y, Sc, La and Lu), which can present their potentials for the green energy applications. The choice of metallic cationic replacements within these structures is greatly influenced their dynamics stability and the ionic character. Among these compounds, SeO3 counterpart is responsible for enhanced optical characteristics. All these compounds have presented wide indirect band gaps from 3.31 eV to 3.93 eV, followed by high values of optical properties like absorption (105 cm−1), optical conductivity (3 fs−1–5 fs−1). Moreover, no transparency is observed for the incident radiations range from 0 eV to 10 eV, which is confirmed by the values ε1(ω) > 0, and n(ω) > 1. Reflectivity remains as low as 10 % within the visible region of incident light which is followed by low loss of dissipated energy within the compounds. Lower value of zero-point energy 0.767 eV for LuSeO3F shows less vibrational frequencies indicating more stability as compared to other compounds. The convergence of heat capacity near the Dulong-Petit limit (74.9 cal/cell. K) reveals the thermal resistance showing potentials for high temperature electronics devices. Ductile nature has been confirmed for XSeO3F (X = Y, Sc, and Lu) compounds by Poisson's and Pugh's ratios, but LaSeO3F compound has demonstrated the more unique auxetic nature. These results suggest that alkaline selenite based oxo-fluoro compounds possess promising potential for next generation green technologies such as optoelectronic, tendon cells, and sustainable energy conversion devices.
{"title":"Multifunctional behavior of alkaline selenite oxo-fluoro compounds, investigated by DFT for green tech applications","authors":"Nawishta Jabeen , Ali Yaqoob , Ahmad Hussain , Aseel Smerat , Mohamed A. Nassan , Nidhal Ben Khedher","doi":"10.1016/j.ica.2025.123046","DOIUrl":"10.1016/j.ica.2025.123046","url":null,"abstract":"<div><div>DFT based simulations have been performed to investigate the structural, optoelectronics, thermodynamics and mechanical properties of double anionic structured (alkaline selenite oxo-fluoro) compounds (XSeO<sub>3</sub>F where X = Y, Sc, La and Lu), which can present their potentials for the green energy applications. The choice of metallic cationic replacements within these structures is greatly influenced their dynamics stability and the ionic character. Among these compounds, SeO<sub>3</sub> counterpart is responsible for enhanced optical characteristics. All these compounds have presented wide indirect band gaps from 3.31 eV to 3.93 eV, followed by high values of optical properties like absorption (10<sup>5</sup> cm<sup>−1</sup>), optical conductivity (3 fs<sup>−1</sup>–5 fs<sup>−1</sup>). Moreover, no transparency is observed for the incident radiations range from 0 eV to 10 eV, which is confirmed by the values ε<sub>1</sub>(ω) > 0, and n(ω) > 1. Reflectivity remains as low as 10 % within the visible region of incident light which is followed by low loss of dissipated energy within the compounds. Lower value of zero-point energy 0.767 eV for LuSeO<sub>3</sub>F shows less vibrational frequencies indicating more stability as compared to other compounds. The convergence of heat capacity near the Dulong-Petit limit (74.9 cal/cell. K) reveals the thermal resistance showing potentials for high temperature electronics devices. Ductile nature has been confirmed for XSeO<sub>3</sub>F (X = Y, Sc, and Lu) compounds by Poisson's and Pugh's ratios, but LaSeO<sub>3</sub>F compound has demonstrated the more unique auxetic nature. These results suggest that alkaline selenite based oxo-fluoro compounds possess promising potential for next generation green technologies such as optoelectronic, tendon cells, and sustainable energy conversion devices.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123046"},"PeriodicalIF":3.2,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A Schiff base ligand, [4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol], shortly Diformyl Amino Pyridine (DAP), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg2+ binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 108 M−1 and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe DAP was converted into a heterogeneous solid-state material, ZnAl2O4 (ZA) conjugated DAP (ZDAP), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to DAP's quenching, ZDAP exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg2+ binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (ZDAP), causing a bathochromic shift in emission. The observed fluorescence quenching of DAP upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, ZDAP demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.
希夫碱配体[4-甲基-2,6-双(（E)-（（2-（吡啶-2-基）乙基）亚氨基）甲基）苯酚]，简称二甲酰氨基吡啶（DAP），是一种均相探针，并通过不同的光谱技术进行了表征。它的荧光被Hg2+结合猝灭，这一过程受多种非辐射途径的控制，包括光诱导电子转移（PET）和重原子效应，Stern-Volmer常数为8.83 × 108 M−1，检测限为1.35 μM。为了解决可重复使用性和样品基质分离等限制，通过将亚胺配体锚定在ZA尖晶石上，将均相探针DAP转化为非均相固态材料ZnAl2O4 （ZA）共轭DAP （ZDAP）。令人惊讶的是，这种改变从根本上改变了感知机制。与DAP的猝灭相反，ZDAP通过聚集诱导发射（AIE）表现出“开启”反应，其中Hg2+结合限制了分子内运动并增强了荧光。该方法的检出限为1.01 nM。ICP-MS分析证实，使用该传感器处理后，汞几乎完全去除，汞去除率高达98.46%。这两个系统的传感机制已经通过DFT计算和实验技术，如斯特恩-沃尔默分析和时间分辨荧光光谱得到证实。理论计算结果与实验结果非常吻合，能隙从2.28 eV （ZA）减小到2.15 eV (ZDAP)，引起发射的深色偏移。所观察到的DAP锚定在ZA上的荧光猝灭是由强配-金属相互作用、电荷转移诱导的非辐射衰变、结构硬化和表面缺陷捕获引起的，与实验（2.93 eV）带隙一致。至关重要的是，ZDAP具有出色的可重复使用性，在螯合剂再生后至少可以保持其传感效率和结构完整性5个循环。这项工作展示了单个希夫基平台如何设计为提供两种互补的传感模式，为汞检测和去除提供敏感，选择性和可持续的解决方案。
{"title":"Concurrent detection and removal of Hg2+ from potable water using ZnAl2O4 modified end off Schiff base ligand: Experimental and theoretical investigation","authors":"Sneha Biswas , Jaydeep Adhikary , Rama Rathi , Sreejeeb Ganguly , Ennio Zangrando , Abhijit Kumar Das","doi":"10.1016/j.ica.2025.123045","DOIUrl":"10.1016/j.ica.2025.123045","url":null,"abstract":"<div><div>A Schiff base ligand, <em>[4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol]</em>, shortly Diformyl Amino Pyridine (<strong>DAP</strong>), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg<sup>2+</sup> binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 10<sup>8</sup> M<sup>−1</sup> and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe <strong>DAP</strong> was converted into a heterogeneous solid-state material, ZnAl<sub>2</sub>O<sub>4</sub> (<strong>ZA</strong>) conjugated <strong>DAP</strong> (<strong>ZDAP</strong>), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to <strong>DAP</strong>'s quenching, <strong>ZDAP</strong> exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg<sup>2+</sup> binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (<strong>ZDAP</strong>), causing a bathochromic shift in emission. The observed fluorescence quenching of <strong>DAP</strong> upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, <strong>ZDAP</strong> demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123045"},"PeriodicalIF":3.2,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839361","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}
Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg2+, Cu2+, Zn2+, Ag+, Al3+, Pb2+,Fe3+,Cd2+, Au3+, Pd2+, Ni2+, Cr3+, Ga3+, Zr4+ as well as anions including I−, F− and CN−. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.
{"title":"Thiophene based chemosensors: a comprehensive review on synthesis and detection of cations and anions","authors":"Zuverya Zareen , Aram Rahman , Anzar Jahan , Salahuddin Syed , Mohammad Arifuddin","doi":"10.1016/j.ica.2025.123042","DOIUrl":"10.1016/j.ica.2025.123042","url":null,"abstract":"<div><div>Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ag<sup>+</sup>, Al<sup>3+</sup>, Pb<sup>2+</sup>,Fe<sup>3+</sup>,Cd<sup>2+</sup>, Au<sup>3+</sup>, Pd<sup>2+</sup>, Ni<sup>2+</sup>, Cr<sup>3+</sup>, Ga<sup>3+</sup>, Zr<sup>4+</sup> as well as anions including I<sup>−</sup>, F<sup>−</sup> and CN<sup>−</sup>. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123042"},"PeriodicalIF":3.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882482","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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