Pub Date : 2026-01-12DOI: 10.1016/j.poly.2026.117964
Zifa Shi , Yu Chen , Xiaoxiang Fan , Hongyu Wang , Jinzhong Gu
In this study, a new series of 1D and 2D coordination polymers (CPs) was hydrothermally assembled from metal(II) chlorides and 4,4′,4″-((benzene-1,3,5-tricarbonyl)tris(azanediyl))tribenzoic acid (H3btta) as a flexible and little explored tetracarboxylate linker. Additionally, several types of aromatic N,N-donor auxiliary ligands were used to promote crystallization, namely 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), bis(4-pyridyl)amin (bpa), 1,4-bis(pyrid-4-yl)benzene (bpb), or 1,2-di(4-pyridyl)ethane (dpe). The obtained products were fully characterized and identified as [Cd(μ3-Hbtta)(H2O)]n⋅4nH2O (1), [Mn(μ3-Hbtta)(2,2΄-bipy)]n (2), [Mn(μ3-Hbtta)(μ-bpb)]n⋅nbpb⋅0.5nH2O (3), [Zn(μ3-Hbtta)(bpb)(H2O)]n⋅0.5nbpb⋅2nH2O (4), [Mn(μ3-Hbtta)(μ-dpe)]n⋅2nH2O (5) [Co(μ3-btta)(Hbpa)(H2O)]n⋅2nH2O (6), and [Zn(μ3-btta)(4,4΄-Hbipy)]n⋅2nH2O (7). Their structural and topological features were also explored, allowing to identify a diversity of 1D chains and 2D coordination networks. Remarkably, coordination polymer 2, 4, and 7 revealed high catalytic activity and reusability in the condensation reaction between benzaldehyde and malononitrile, leading to almost quantitative product yields (>99%) under optimized conditions. The present work contributes to widening the family of CPs assembled from flexible polycarboxylate linkers and highlights promising application of these compounds in heterogeneous catalysis.
{"title":"Coordination polymers of Mn(II), Co(II), Zn(II), and Cd(II) driven by amidocarboxylates: Hydrothermal syntheses, structural features, and catalytic application","authors":"Zifa Shi , Yu Chen , Xiaoxiang Fan , Hongyu Wang , Jinzhong Gu","doi":"10.1016/j.poly.2026.117964","DOIUrl":"10.1016/j.poly.2026.117964","url":null,"abstract":"<div><div>In this study, a new series of 1D and 2D coordination polymers (CPs) was hydrothermally assembled from metal(II) chlorides and 4,4′,4″-((benzene-1,3,5-tricarbonyl)tris(azanediyl))tribenzoic acid (H<sub>3</sub>btta) as a flexible and little explored tetracarboxylate linker. Additionally, several types of aromatic N,N-donor auxiliary ligands were used to promote crystallization, namely 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), bis(4-pyridyl)amin (bpa), 1,4-bis(pyrid-4-yl)benzene (bpb), or 1,2-di(4-pyridyl)ethane (dpe). The obtained products were fully characterized and identified as [Cd(<em>μ</em><sub>3</sub><em>-</em>Hbtta)(H<sub>2</sub>O)]<sub><em>n</em></sub>⋅4<em>n</em>H<sub>2</sub>O (<strong>1</strong>), [Mn(<em>μ</em><sub>3</sub><em>-</em>Hbtta)(2,2΄-bipy)]<sub><em>n</em></sub> (<strong>2</strong>), [Mn(<em>μ</em><sub>3</sub><em>-</em>Hbtta)(<em>μ-</em>bpb)]<sub><em>n</em></sub>⋅<em>n</em>bpb⋅0.5<em>n</em>H<sub>2</sub>O (<strong>3</strong>), [Zn(<em>μ</em><sub>3</sub><em>-</em>Hbtta)(bpb)(H<sub>2</sub>O)]<sub><em>n</em></sub>⋅0.5<em>n</em>bpb⋅2<em>n</em>H<sub>2</sub>O (<strong>4</strong>), [Mn(<em>μ</em><sub>3</sub><em>-</em>Hbtta)(<em>μ-</em>dpe)]<sub><em>n</em></sub>⋅2<em>n</em>H<sub>2</sub>O (<strong>5</strong>) [Co(<em>μ</em><sub>3</sub><em>-</em>btta)(Hbpa)(H<sub>2</sub>O)]<sub><em>n</em></sub>⋅2<em>n</em>H<sub>2</sub>O (<strong>6</strong>), and [Zn(<em>μ</em><sub>3</sub><em>-</em>btta)(4,4΄-Hbipy)]<sub><em>n</em></sub>⋅2<em>n</em>H<sub>2</sub>O (<strong>7</strong>). Their structural and topological features were also explored, allowing to identify a diversity of 1D chains and 2D coordination networks. Remarkably, coordination polymer <strong>2</strong>, <strong>4</strong>, and <strong>7</strong> revealed high catalytic activity and reusability in the condensation reaction between benzaldehyde and malononitrile, leading to almost quantitative product yields (>99%) under optimized conditions. The present work contributes to widening the family of CPs assembled from flexible polycarboxylate linkers and highlights promising application of these compounds in heterogeneous catalysis.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117964"},"PeriodicalIF":2.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145980206","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 : 2026-01-07DOI: 10.1016/j.poly.2025.117952
John Williams D
This manuscript aims to develop the PCz/MnO2/GO (PMG) p–n–p heterojunction harnessing UV and natural sunlight irradiation for the degradation of dyes. The synthesized PCz, MnO2, GO, MnO2/GO (MG) and PMG were exposed to XRD studies which exhibited the primitive tetragonal structure. The UV spectrum of PMG exhibited a peak at 336 nm which has the potential to absorb the UV and direct sunlight. The PMG manifested non-uniform spherical like morphology and demonstrated higher thermal stability than the MG and PCz. The PMG exhibited enhanced photo catalytic performance towards congo red (CR) dye under UV (97.5%) and natural sunlight (98.5%) irradiation. The rate constants (k) of PMG was 0.09755 which is 2.29 times greater than GO (0.04246) under identical conditions. Electrochemical impedance spectroscopy study under light medium reveals smaller arc radius for the excellent electron-hole separation. The PL study discloses that the PMG heterojunction was highly efficient in the separation of charge carriers. The ESR study shows that the superoxide and hole were the major radicals involved in the degradation of PMG. Furthermore, the heterojunction revealed exceptional stability after four successive cycles with only a 3–7% loss in photocatalytic efficiency. The prepared p–n–p heterojunction could be used as a valuable photocatalysts which intimidate the toxic waste products from the textile industries.
{"title":"Facile synthesis of PCz/MnO2/GO heterojunction for enhanced photocatalytic activity towards congo red dye under various light irradiations","authors":"John Williams D","doi":"10.1016/j.poly.2025.117952","DOIUrl":"10.1016/j.poly.2025.117952","url":null,"abstract":"<div><div>This manuscript aims to develop the PCz/MnO<sub>2</sub>/GO (PMG) p–n–p heterojunction harnessing UV and natural sunlight irradiation for the degradation of dyes. The synthesized PCz, MnO<sub>2</sub>, GO, MnO<sub>2</sub>/GO (MG) and PMG were exposed to XRD studies which exhibited the primitive tetragonal structure. The UV spectrum of PMG exhibited a peak at 336 nm which has the potential to absorb the UV and direct sunlight. The PMG manifested non-uniform spherical like morphology and demonstrated higher thermal stability than the MG and PCz. The PMG exhibited enhanced photo catalytic performance towards congo red (CR) dye under UV (97.5%) and natural sunlight (98.5%) irradiation. The rate constants (k) of PMG was 0.09755 which is 2.29 times greater than GO (0.04246) under identical conditions. Electrochemical impedance spectroscopy study under light medium reveals smaller arc radius for the excellent electron-hole separation. The PL study discloses that the PMG heterojunction was highly efficient in the separation of charge carriers. The ESR study shows that the superoxide and hole were the major radicals involved in the degradation of PMG. Furthermore, the heterojunction revealed exceptional stability after four successive cycles with only a 3–7% loss in photocatalytic efficiency. The prepared p–n–p heterojunction could be used as a valuable photocatalysts which intimidate the toxic waste products from the textile industries.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117952"},"PeriodicalIF":2.6,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145929094","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 : 2026-01-05DOI: 10.1016/j.poly.2026.117955
Adnan S. Abu-Surrah , Jumana Ayyad , Lubna H. Tahtamouni , Musa I. El-Barghouthi , Hassan Abul-Futouh , Wiam Al-Sharaa , Raed A. Ghanem
A series of water-soluble mixed-ligands iron(III) (1–3), ruthenium(III) (4, 5), and cobalt(III) (6–8) complexes bearing amino acids and heterocyclic diimine ligands, with the general formula [M(AA)2(NN)]Cl, where (M = Fe, Ru, and Co); (AA = L-leucine, leu; L-glutamic acid, glu); (N-N = 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen)) were synthesized. The complexes were characterized using elemental analysis, molar conductivity, IR, UV–Vis spectroscopy, and fluorescence spectroscopy. According to the analytical data and structural analysis using density functional theory (DFT) of the complexes, the mixed ligands formed a distorted octahedral geometry around the metal center.
The in vitro antiproliferative activities of the complexes were evaluated against three human breast cancer cell lines (BT549, MCF-7, and T47D). Leucine-based iron(III), ruthenium(III), and cobalt(III) complexes containing 1,10-phenanthroline (2, 5, and 7, respectively) exhibited higher cytotoxicity against all studied breast cancer cell lines than the corresponding bipyridine-based complexes. Moreover, these complexes showed cancer selectivity against the non-malignant MCF10A cells. Among the studied complexes, complex 2, containing leucine and 1,10-phenanthroline moieties, exhibited the most potent cytotoxicity against the tested cancer cells, showing activity comparable to that of cisplatin against BT549 and MCF-7 breast cancer cell lines (IC50 = 23.4 μM and 20.4 μM, vs 34.2 μM and 31.3 μM respectively). Consequently, complex 2 was selected for molecular docking studies to investigate its interactions and inhibition of receptor tyrosine kinases (EGFR and HER2) and estrogen receptor alpha (ERα).
{"title":"Iron(III), ruthenium(III), and cobalt(III) complexes bearing diimines and amino acids as potent anticancer agents: synthesis, DFT, molecular docking, and biological activity","authors":"Adnan S. Abu-Surrah , Jumana Ayyad , Lubna H. Tahtamouni , Musa I. El-Barghouthi , Hassan Abul-Futouh , Wiam Al-Sharaa , Raed A. Ghanem","doi":"10.1016/j.poly.2026.117955","DOIUrl":"10.1016/j.poly.2026.117955","url":null,"abstract":"<div><div>A series of water-soluble mixed-ligands iron(III) <strong>(1</strong>–<strong>3)</strong>, ruthenium(III) <strong>(4, 5)</strong>, and cobalt(III) <strong>(6</strong>–<strong>8)</strong> complexes bearing amino acids and heterocyclic diimine ligands, with the general formula [M(AA)<sub>2</sub>(N<img>N)]Cl, where (M = Fe, Ru, and Co); (AA = L-leucine, leu; L-glutamic acid, glu); (N-<em>N</em> = 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen)) were synthesized. The complexes were characterized using elemental analysis, molar conductivity, IR, UV–Vis spectroscopy, and fluorescence spectroscopy. According to the analytical data and structural analysis using density functional theory (DFT) of the complexes, the mixed ligands formed a distorted octahedral geometry around the metal center.</div><div>The <em>in vitro</em> antiproliferative activities of the complexes were evaluated against three human breast cancer cell lines (BT549, MCF-7, and T47D). Leucine-based iron(III), ruthenium(III), and cobalt(III) complexes containing 1,10-phenanthroline (<strong>2</strong>, <strong>5</strong>, and <strong>7</strong>, respectively) exhibited higher cytotoxicity against all studied breast cancer cell lines than the corresponding bipyridine-based complexes. Moreover, these complexes showed cancer selectivity against the non-malignant MCF10A cells. Among the studied complexes, complex <strong>2</strong>, containing leucine and 1,10-phenanthroline moieties, exhibited the most potent cytotoxicity against the tested cancer cells, showing activity comparable to that of cisplatin against BT549 and MCF-7 breast cancer cell lines (IC<sub>50</sub> = 23.4 μM and 20.4 μM, <em>vs</em> 34.2 μM and 31.3 μM respectively). Consequently, complex <strong>2</strong> was selected for molecular docking studies to investigate its interactions and inhibition of receptor tyrosine kinases (EGFR<!--> <!-->and HER2) and estrogen receptor alpha (ERα).</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117955"},"PeriodicalIF":2.6,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145929092","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 : 2026-01-03DOI: 10.1016/j.poly.2025.117954
Václav Ráliš , Kamila Dostálová , Jiří Kubišta , Róbert Gyepes , Vojtěch Hamala , Roman Hrstka , Jiří Pinkas
Conventional chemotherapy often lacks specificity, leading to significant side effects and highlighting the need for more targeted cancer therapies. The overexpression of cyclooxygenase (COX) enzymes in various malignancies, including colorectal cancer, makes COX inhibition a promising therapeutic strategy. Non-steroidal anti-inflammatory drugs (NSAIDs), such as Ibuprofen, are well-known COX inhibitors. In this study, we synthesized two types of cyclopentadienyl-arene ruthenium (CAR)–Ibuprofen conjugates: compounds 1–5, featuring η6-coordinated Ibuprofen derivatives, and compound 7, with Ibuprofen attached via an ester linkage to the complex periphery. Cytotoxicity assays against colorectal cancer cell lines (SW-620, SW-480) and non-cancerous HEK-293 cells revealed that compounds 1, 5, and 7 exhibit anti-proliferative activity in the low micromolar range, although without selectivity. These complexes also showed effective inhibition of COX enzymatic activity. Western blot analysis indicated that their primary mechanism involves induction of cell cycle arrest, rather than activation of apoptotic or autophagic pathways.
{"title":"Ibuprofen-conjugated cyclopentadienyl–arene ruthenium complexes induce cytostatic effects and COX inhibition in colorectal cancer cells","authors":"Václav Ráliš , Kamila Dostálová , Jiří Kubišta , Róbert Gyepes , Vojtěch Hamala , Roman Hrstka , Jiří Pinkas","doi":"10.1016/j.poly.2025.117954","DOIUrl":"10.1016/j.poly.2025.117954","url":null,"abstract":"<div><div>Conventional chemotherapy often lacks specificity, leading to significant side effects and highlighting the need for more targeted cancer therapies. The overexpression of cyclooxygenase (COX) enzymes in various malignancies, including colorectal cancer, makes COX inhibition a promising therapeutic strategy. Non-steroidal anti-inflammatory drugs (NSAIDs), such as Ibuprofen, are well-known COX inhibitors. In this study, we synthesized two types of cyclopentadienyl-arene ruthenium (CAR)–Ibuprofen conjugates: compounds <strong>1</strong>–<strong>5</strong>, featuring η<sup>6</sup>-coordinated Ibuprofen derivatives, and compound <strong>7</strong>, with Ibuprofen attached <em>via</em> an ester linkage to the complex periphery. Cytotoxicity assays against colorectal cancer cell lines (SW-620, SW-480) and non-cancerous HEK-293 cells revealed that compounds <strong>1</strong>, <strong>5</strong>, and <strong>7</strong> exhibit anti-proliferative activity in the low micromolar range, although without selectivity. These complexes also showed effective inhibition of COX enzymatic activity. Western blot analysis indicated that their primary mechanism involves induction of cell cycle arrest, rather than activation of apoptotic or autophagic pathways.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117954"},"PeriodicalIF":2.6,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915217","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}
Five novel cadmium(II) coordination complexes incorporating 9-anthracenecarboxylic acid and 4-vinylpyridine derived ligands, [Cd(9AC)2(4spy)2(MeOH)]·MeOH (1), [Cd(9AC)2(3tpy)2(MeOH)]·MeOH (2), [Cd(9AC)2(2tpy)2(MeOH)]·MeOH (3), [Cd2(9AC)4(2tpy)(MeOH)3] (4), and [Cd(9AC)4]·2(H-2tpy) (5) (where 9AC = 9-anthracenecarboxylate, 4spy = 4-styrylpyridine, 3tpy = 4-(2-(thiophen-3-yl)vinyl)pyridine, 2tpy = 4-(2-(thiophen-2-yl)vinyl)pyridine, MeOH = methanol) have been synthesized and characterized by single-crystal X-ray diffraction. Their UV–visible absorption, luminescence, and thermal properties were examined. Compounds 1, 2 and 3 depicted structural similarity where these compounds have N and O atoms coordinated to Cd from the 4-vinylpyridine-derived ligands, methanol and 9AC ligand, along with one lattice methanol. This methanol molecule formed H-bond with neighboring Cd complex and this way the chain structure is propagated. Compounds 2 and 3 are isostructural in nature whereas 1 has shown low packing similarity. This similarity is mainly derived by the benzene-thiophene exchange rule as well as positional change of S atom. The influence of methanol on the formation of supramolecular chains propagating in opposite directions analogous to that of DNA strands. All these compounds displayed comparable thermal stability, optical characteristics, and structural features. Meanwhile, 4 and 5 have different stoichiometry and structural packing attributed to the variable coordination geometries accessible to cadmium. Hirshfeld surface analysis highlighted the significant role of van der Waals interactions in crystal packing, and these structures would be interesting to understand the role of solvent, metal geometries and solid-state packing.
{"title":"Methanol-templated supramolecular assembly in cadmium(II)-anthracene-vinylpyridyl complexes: from isostructurality to photophysical behavior","authors":"Devendra Dewangan , Uma Kurakula , Smita Singh , Sesha Vempati , Raghavender Medishetty","doi":"10.1016/j.poly.2025.117953","DOIUrl":"10.1016/j.poly.2025.117953","url":null,"abstract":"<div><div>Five novel cadmium(II) coordination complexes incorporating 9-anthracenecarboxylic acid and 4-vinylpyridine derived ligands, [Cd(9AC)<sub>2</sub>(4spy)<sub>2</sub>(MeOH)]·MeOH (<strong>1</strong>), [Cd(9AC)<sub>2</sub>(3tpy)<sub>2</sub>(MeOH)]·MeOH (<strong>2</strong>), [Cd(9AC)<sub>2</sub>(2tpy)<sub>2</sub>(MeOH)]·MeOH (<strong>3</strong>), [Cd<sub>2</sub>(9AC)<sub>4</sub>(2tpy)(MeOH)<sub>3</sub>] (<strong>4</strong>), and [Cd(9AC)<sub>4</sub>]·2(H-2tpy) (<strong>5</strong>) (where 9AC = 9-anthracenecarboxylate, 4spy = 4-styrylpyridine, 3tpy = 4-(2-(thiophen-3-yl)vinyl)pyridine, 2tpy = 4-(2-(thiophen-2-yl)vinyl)pyridine, MeOH = methanol) have been synthesized and characterized by single-crystal X-ray diffraction. Their UV–visible absorption, luminescence, and thermal properties were examined. Compounds <strong>1</strong>, <strong>2</strong> and <strong>3</strong> depicted structural similarity where these compounds have N and O atoms coordinated to Cd from the 4-vinylpyridine-derived ligands, methanol and 9AC ligand, along with one lattice methanol. This methanol molecule formed H-bond with neighboring Cd complex and this way the chain structure is propagated. Compounds <strong>2</strong> and <strong>3</strong> are isostructural in nature whereas <strong>1</strong> has shown low packing similarity. This similarity is mainly derived by the benzene-thiophene exchange rule as well as positional change of S atom. The influence of methanol on the formation of supramolecular chains propagating in opposite directions analogous to that of DNA strands. All these compounds displayed comparable thermal stability, optical characteristics, and structural features. Meanwhile, <strong>4</strong> and <strong>5</strong> have different stoichiometry and structural packing attributed to the variable coordination geometries accessible to cadmium. Hirshfeld surface analysis highlighted the significant role of van der Waals interactions in crystal packing, and these structures would be interesting to understand the role of solvent, metal geometries and solid-state packing.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117953"},"PeriodicalIF":2.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915218","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.poly.2025.117951
Marko Pešić , Jovana Bugarinović , Slađana B. Novaković , Goran A. Bogdanović , Anka Todosijević , Dragana Stevanović , Ivan Damljanović
A new series of ferrocene-containing pyrrolidine derivatives was synthesized through a [3+2] dipolar cycloaddition of azomethine ylides with 1-ferrocenyl-2-nitroethene. Under mild conditions and in the presence of silver acetate and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the reaction was performed repeatedly to afford six novel compounds in moderate to good yields. Structural elucidation was achieved by NMR and IR, while single-crystal X-ray diffraction of two representative compounds unambiguously confirmed the stereochemical outcome and spatial orientation of the substituents. The stereochemical preferences were rationalized by charge distribution, steric effects of the bulky ferrocene group, and secondary orbital interactions, consistent with an endo reaction pathway. According to X-ray analysis, all five substituents of the pyrrolidine ring are involved in intermolecular interactions, while a double chain composed solely of ferrocenyl units appears as the most prominent structural feature. The non-covalent interactions were analyzed based on interaction energy. Electrochemical properties were examined by cyclic voltammetry (CV), which revealed a reversible one-electron redox process. The anodic peak potentials were shifted relative to ferrocene, reflecting the influence of electron-withdrawing nitro substituents. These findings highlight the dual synthetic and biological relevance of ferrocenyl pyrrolidines as redox-active scaffolds with antioxidant potential.
{"title":"Stereoselective synthesis and redox properties of ferrocene-substituted pyrrolidines via [3+2] cycloaddition","authors":"Marko Pešić , Jovana Bugarinović , Slađana B. Novaković , Goran A. Bogdanović , Anka Todosijević , Dragana Stevanović , Ivan Damljanović","doi":"10.1016/j.poly.2025.117951","DOIUrl":"10.1016/j.poly.2025.117951","url":null,"abstract":"<div><div>A new series of ferrocene-containing pyrrolidine derivatives was synthesized through a [3+2] dipolar cycloaddition of azomethine ylides with 1-ferrocenyl-2-nitroethene. Under mild conditions and in the presence of silver acetate and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the reaction was performed repeatedly to afford six novel compounds in moderate to good yields. Structural elucidation was achieved by NMR and IR, while single-crystal X-ray diffraction of two representative compounds unambiguously confirmed the stereochemical outcome and spatial orientation of the substituents. The stereochemical preferences were rationalized by charge distribution, steric effects of the bulky ferrocene group, and secondary orbital interactions, consistent with an <em>endo</em> reaction pathway. According to X-ray analysis, all five substituents of the pyrrolidine ring are involved in intermolecular interactions, while a double chain composed solely of ferrocenyl units appears as the most prominent structural feature. The non-covalent interactions were analyzed based on interaction energy. Electrochemical properties were examined by cyclic voltammetry (CV), which revealed a reversible one-electron redox process. The anodic peak potentials were shifted relative to ferrocene, reflecting the influence of electron-withdrawing nitro substituents. These findings highlight the dual synthetic and biological relevance of ferrocenyl pyrrolidines as redox-active scaffolds with antioxidant potential.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"286 ","pages":"Article 117951"},"PeriodicalIF":2.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145885399","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.poly.2025.117950
Tau S. Ntelane , Mayetu Segale , Nomcebo H. Mthombeni , Dieketseng Tsotetsi , Mokhotjwa Dhlamini , Usisipho Feleni , Rudzani Sigwadi , Alex T. Kuvarega
Developing novel adsorbents with high selectivity is crucial for the effective adsorption of diverse organic pollutants in wastewater. Dendritic fibrous nanosilica (KCC-1) was synthesized through the hydrothermal method to evaluate the impact of varying silica content (112, 170 and 224 mmol) on its adsorption capacity. The resultant KCC-1 displayed distinctly defined fibres and three-dimensional (3D) center-radial channels, resulting in large pore volumes, exceedingly high specific surface areas, and particularly accessible internal sites, which offer numerous adsorption sites. Experimental results demonstrated that varying silica moles affected particle size and specific textural properties (including surface area and pore volume) to a certain degree, with little impact on the performance. The results indicated that the synthesized KCC-1 using 170 mmol silica source exhibited superior efficiency for the selective adsorption of cationic dyes (rhodamine B and methylene blue) compared to anionic dyes (methyl orange and tartrazine) at pH 7.0. The maximum adsorption capacities for rhodamine B and methylene blue, according to the Langmuir isotherm model, were found to be 124.5 mg/g and 117.4 mg/g, respectively. The pronounced adsorption affinity for cationic dyes was attributed to the robust electrostatic interactions that occur between the adsorbent and the adsorbates. This study elucidates the extent to which reaction parameters influence the performance of KCC-1, given that their physicochemical properties are contingent with methodology and reaction parameters. The KCC-1 exhibits a remarkable ability to selectively remove dyes, indicating significant potential for the separation and recovery of dyes from real wastewater.
{"title":"Selective removal of cationic organic dyes from aqueous solution using dendritic fibrous nanosilica","authors":"Tau S. Ntelane , Mayetu Segale , Nomcebo H. Mthombeni , Dieketseng Tsotetsi , Mokhotjwa Dhlamini , Usisipho Feleni , Rudzani Sigwadi , Alex T. Kuvarega","doi":"10.1016/j.poly.2025.117950","DOIUrl":"10.1016/j.poly.2025.117950","url":null,"abstract":"<div><div>Developing novel adsorbents with high selectivity is crucial for the effective adsorption of diverse organic pollutants in wastewater. Dendritic fibrous nanosilica (KCC-1) was synthesized through the hydrothermal method to evaluate the impact of varying silica content (112, 170 and 224 mmol) on its adsorption capacity. The resultant KCC-1 displayed distinctly defined fibres and three-dimensional (3D) center-radial channels, resulting in large pore volumes, exceedingly high specific surface areas, and particularly accessible internal sites, which offer numerous adsorption sites. Experimental results demonstrated that varying silica moles affected particle size and specific textural properties (including surface area and pore volume) to a certain degree, with little impact on the performance. The results indicated that the synthesized KCC-1 using 170 mmol silica source exhibited superior efficiency for the selective adsorption of cationic dyes (rhodamine B and methylene blue) compared to anionic dyes (methyl orange and tartrazine) at pH 7.0. The maximum adsorption capacities for rhodamine B and methylene blue, according to the Langmuir isotherm model, were found to be 124.5 mg/g and 117.4 mg/g, respectively. The pronounced adsorption affinity for cationic dyes was attributed to the robust electrostatic interactions that occur between the adsorbent and the adsorbates. This study elucidates the extent to which reaction parameters influence the performance of KCC-1, given that their physicochemical properties are contingent with methodology and reaction parameters. The KCC-1 exhibits a remarkable ability to selectively remove dyes, indicating significant potential for the separation and recovery of dyes from real wastewater.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"286 ","pages":"Article 117950"},"PeriodicalIF":2.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145885397","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 : 2025-12-26DOI: 10.1016/j.poly.2025.117941
Ji-Sheng Wang, Yi-Ming Li, Yu Bai, Xiang Wang
To exploit polyoxometalate−based inorganic−organic hybrid compounds having potential capacitive and catalytic performances, in this work, 3, 5-bis(1H-imidazol-1-yl)nitrobenzene (BINB) and 1, 3-bis(3-(2-pyridyl)pyrazole)nitrobenzene (BPPNB) were used as bidentate and bis-bidentate organic ligands, and two hybrid copper compounds based on polymolybdates formulated as [Cu(H2O)2][Cu(BINB)2][β-Mo8O26]·4H2O (1) and [Cu4(BPPNB)2][γ-Mo8O26]2·8H2O (2), were synthesized under hydrothermal conditions and characterized. Two compounds have two−dimensional layer structures. The ring-connected-ring metal-organic chains constructed from bidentate BINB ligands and Cu2+ ions gathered Cu/[β-Mo8O26]4− inorganic chains, resulting in a two−dimensional layer of 1. In 2, the [γ-Mo8O26]4− polymolybdates were connected each other in an edge−shared manner, giving a kind of polyoxometalate−based inorganic chains, further linked by bis-bidentate BPPNB ligands via Cu2+ ions into a two−dimensional structure. Two compounds as electrode materials exhibited enhanced specific capacitances of 1462 F g−1 for 1, 1530 F g−1 for 2 at a current density of 1 A g−1. Moreover, 1 and 2 were efficient in catalytic detoxification of sulfur mustard simulant 2-chloroethyl ethyl sulfide with satisfying conversion rates and selectivity. These results provided a promising strategy in the exploitation polyoxometalate−based hybrids as capacitor materials and catalysts.
为了开发具有潜在电容和催化性能的多金属氧酸盐基无机-有机杂化化合物，本研究以3,5 -双（h -咪唑-1-基）硝基苯（BINB）和1,3 -双（3-（2-吡啶基）吡唑）硝基苯（BPPNB）为双齿和双齿有机配体，并以两种多钼酸盐为基础的杂化铜化合物配制为[Cu(H2O)2][Cu(BINB)2][β-Mo8O26]·4H2O(1)和[Cu4(BPPNB)2][γ-Mo8O26]2·8H2O(2)。在水热条件下合成并表征。两种化合物具有二维层状结构。由双齿BINB配体和Cu2+离子构建的环连接环金属有机链聚集Cu/[β-Mo8O26]4 -无机链，形成1的二维层。在2中，[γ-Mo8O26]4 -多钼酸盐以共享边的方式相互连接，形成了一种基于多金属氧酸盐的无机链，并通过Cu2+离子进一步由双双齿BPPNB配体连接成二维结构。两种化合物作为电极材料，在电流密度为1 a g−1时，比电容分别为1462 F g−1和1530 F g−1。此外，1和2在芥菜模拟物2-氯乙基乙基硫醚的催化解毒中具有良好的转化率和选择性。这些结果为开发多金属酸氧基杂化材料作为电容器材料和催化剂提供了一条有前途的策略。
{"title":"Bidentate/bis-bidentate ligands−contained polymolybdate−based hybrid copper compounds for capacitive performance and catalytic detoxification of sulfur mustard simulant","authors":"Ji-Sheng Wang, Yi-Ming Li, Yu Bai, Xiang Wang","doi":"10.1016/j.poly.2025.117941","DOIUrl":"10.1016/j.poly.2025.117941","url":null,"abstract":"<div><div>To exploit polyoxometalate−based inorganic−organic hybrid compounds having potential capacitive and catalytic performances, in this work, 3, 5-bis(1H-imidazol-1-yl)nitrobenzene (BINB) and 1, 3-bis(3-(2-pyridyl)pyrazole)nitrobenzene (BPPNB) were used as bidentate and bis-bidentate organic ligands, and two hybrid copper compounds based on polymolybdates formulated as [Cu(H<sub>2</sub>O)<sub>2</sub>][Cu(BINB)<sub>2</sub>][β-Mo<sub>8</sub>O<sub>26</sub>]·4H<sub>2</sub>O (<strong>1</strong>) and [Cu<sub>4</sub>(BPPNB)<sub>2</sub>][γ-Mo<sub>8</sub>O<sub>26</sub>]<sub>2</sub>·8H<sub>2</sub>O (<strong>2</strong>), were synthesized under hydrothermal conditions and characterized. Two compounds have two−dimensional layer structures. The ring-connected-ring metal-organic chains constructed from bidentate BINB ligands and Cu<sup>2+</sup> ions gathered Cu/[β-Mo<sub>8</sub>O<sub>26</sub>]<sup>4−</sup> inorganic chains, resulting in a two−dimensional layer of <strong>1</strong>. In <strong>2</strong>, the [γ-Mo<sub>8</sub>O<sub>26</sub>]<sup>4−</sup> polymolybdates were connected each other in an edge−shared manner, giving a kind of polyoxometalate−based inorganic chains, further linked by bis-bidentate BPPNB ligands via Cu<sup>2+</sup> ions into a two−dimensional structure. Two compounds as electrode materials exhibited enhanced specific capacitances of 1462 F g<sup>−1</sup> for <strong>1</strong>, 1530 F g<sup>−1</sup> for <strong>2</strong> at a current density of 1 A g<sup>−1</sup>. Moreover, <strong>1</strong> and <strong>2</strong> were efficient in catalytic detoxification of sulfur mustard simulant 2-chloroethyl ethyl sulfide with satisfying conversion rates and selectivity. These results provided a promising strategy in the exploitation polyoxometalate−based hybrids as capacitor materials and catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"286 ","pages":"Article 117941"},"PeriodicalIF":2.6,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145885955","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 study, we report the design and synthesis of a novel heterocycle-based hydrazone accomplished via condensation reaction between chloroquinoline hydrazine and heterocyclic carbaldehyde derivatives and the resulting heterocycle-chloroquinoline hydrazone hybrid Schiff base ligands were successfully characterized using spectral techniques. The hybrid probes exhibited remarkable optical responses, showing high sensitivity, selectivity, and rapid detection ability toward Ce3+ ions as studied through UV–visible and fluorescence titration experiments. The probes 3a–3c exhibited low limits of detection (LOD) for Ce(III) established as 6.14 nM, 7.57 nM, 8.57 nM and good binding constant found to be 5.91 × 104 M−1, 1.40 × 104 M−1, and 2.39 × 104 M−1, respectively. The stoichiometric ratio was estimated as (1:1) ratio for metal-ligand complex by Job plot analysis. The DFT calculations were performed using B3LYP/6-311G++(d,p) for free probes and B3LYP/SDD for corresponding metal complexes to provide insights into binding interactions. The integrated experimental and theoretical findings formulate a reliable and precise detection framework for the detection of Ce(III) ions, having potential applications in ecological monitoring and analytical chemistry.
{"title":"Exploring pyrrole, furan, and thiophene-based Schiff bases for selective cerium (III) ion recognition: Experimental and computational investigation","authors":"Sonia Balan , Vijay Kumar , Nancy George , Jandeep Singh , Kashmiri Lal","doi":"10.1016/j.poly.2025.117940","DOIUrl":"10.1016/j.poly.2025.117940","url":null,"abstract":"<div><div>In this study, we report the design and synthesis of a novel heterocycle-based hydrazone accomplished via condensation reaction between chloroquinoline hydrazine and heterocyclic carbaldehyde derivatives and the resulting heterocycle-chloroquinoline hydrazone hybrid Schiff base ligands were successfully characterized using spectral techniques. The hybrid probes exhibited remarkable optical responses, showing high sensitivity, selectivity, and rapid detection ability toward Ce<sup>3+</sup> ions as studied through UV–visible and fluorescence titration experiments. The probes <strong>3a–3c</strong> exhibited low limits of detection (LOD) for Ce(III) established as 6.14 nM, 7.57 nM, 8.57 nM and good binding constant found to be 5.91 × 10<sup>4</sup> M<sup>−1</sup>, 1.40 × 10<sup>4</sup> M<sup>−1</sup>, and 2.39 × 10<sup>4</sup> M<sup>−1</sup>, respectively. The stoichiometric ratio was estimated as (1:1) ratio for metal-ligand complex by Job plot analysis. The DFT calculations were performed using B3LYP/6-311G++(d,p) for free probes and B3LYP/SDD for corresponding metal complexes to provide insights into binding interactions. The integrated experimental and theoretical findings formulate a reliable and precise detection framework for the detection of Ce(III) ions, having potential applications in ecological monitoring and analytical chemistry.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"286 ","pages":"Article 117940"},"PeriodicalIF":2.6,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145885398","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 : 2025-12-24DOI: 10.1016/j.poly.2025.117939
Zarghuna Firdous , Haifa A. Alyousef , B.M. Alotaibi , Albandari.W. Alrowaily , Hala M. Abo-Dief , Ahmed Hussain Jawhari , Abhinav Kumar
In recent decades, research community has experienced a pronounced emphasis on adjustable nanostructured materials for supercapacitors, influenced by the increasing demand for eco-friendly energy sources. To address these challenges via enhancement of electrode constituents, metal oxide-based rGO nanocomposites have exhibited considerable potential in multiple domains, including energy conversion and storage. The current research encompasses the fabrication of MgCrO4/rGO nanohybrid as capacitive material using straightforward hydrothermal method, which yields good morphological and structural properties, as confirmed by various physiochemical and electrochemical techniques. Electrochemical nature of produced nanocomposite is assessed within confined potential window of 0.0–0.6 V vs. Ag/AgCl in 2 M of alkaline medium (KOH). Meanwhile, electrochemical results suggested that specific capacitance (Cs) of MgCrO4/rGO nanocomposite was examined to 1415 F/g @ 1 A/g. Significant Cs of MgCrO4/rGO corresponds to crystal size, increased surface area (SA) of rGO and synergistic impact produced by MgCrO4 and rGO. Furthermore, energy density (44.3 Wh/kg) as well as power density (237.5 W/kg @ 1 A/g) was exhibited by nanocomposite. Additionally, collected results revealed significant effectiveness of ion transport efficiency due to small solution resistance (Rs = 0.90 Ω) at MgCrO4/rGO interface. Diverse stability tests demonstrated that MgCrO4/rGO displayed stable performance over 50 h with strong structure integrity after 3000th cycles. Our outcomes demonstrate that synthesized nanohybrid exhibited remarkable electrochemical functionality and holds great potential for addressing future energy-related challenges.
近几十年来，受环保能源需求增长的影响，研究领域对超级电容器的可调纳米结构材料有了明显的重视。为了通过增强电极成分来解决这些挑战，金属氧化物基氧化石墨烯纳米复合材料在包括能量转换和存储在内的多个领域显示出相当大的潜力。目前的研究包括使用简单的水热法制备MgCrO4/rGO纳米杂化材料作为电容材料，该材料具有良好的形态和结构性能，并得到了各种物理化学和电化学技术的证实。在2 M碱性介质（KOH）中，对制备的纳米复合材料的电化学性质进行了评价，限定电位窗口为0.0-0.6 V vs. Ag/AgCl。同时，电化学结果表明，MgCrO4/rGO纳米复合材料的比电容（Cs）为1415 F/g @ 1 A/g。MgCrO4/rGO的显著Cs与晶体尺寸、增大的rGO表面积（SA）以及MgCrO4和rGO产生的协同影响相对应。此外，纳米复合材料的能量密度为44.3 Wh/kg，功率密度为237.5 W/kg @ 1 A/g。此外，收集的结果表明，由于MgCrO4/rGO界面的溶液阻力小（Rs = 0.90 Ω），离子传输效率显著提高。多种稳定性测试表明，经过3000次循环后，MgCrO4/rGO在50 h内表现出稳定的性能，结构完整性强。我们的研究结果表明，合成的纳米杂化材料具有显著的电化学功能，在解决未来能源相关挑战方面具有巨大的潜力。
{"title":"Hydrothermally fabricated innovative MgCrO4/rGO composite for supercapacitor activities","authors":"Zarghuna Firdous , Haifa A. Alyousef , B.M. Alotaibi , Albandari.W. Alrowaily , Hala M. Abo-Dief , Ahmed Hussain Jawhari , Abhinav Kumar","doi":"10.1016/j.poly.2025.117939","DOIUrl":"10.1016/j.poly.2025.117939","url":null,"abstract":"<div><div>In recent decades, research community has experienced a pronounced emphasis on adjustable nanostructured materials for supercapacitors, influenced by the increasing demand for eco-friendly energy sources. To address these challenges via enhancement of electrode constituents, metal oxide-based rGO nanocomposites have exhibited considerable potential in multiple domains, including energy conversion and storage. The current research encompasses the fabrication of MgCrO<sub>4</sub>/rGO nanohybrid as capacitive material using straightforward hydrothermal method, which yields good morphological and structural properties, as confirmed by various physiochemical and electrochemical techniques. Electrochemical nature of produced nanocomposite is assessed within confined potential window of 0.0–0.6 V vs. Ag/AgCl in 2 M of alkaline medium (KOH). Meanwhile, electrochemical results suggested that specific capacitance (C<sub>s</sub>) of MgCrO<sub>4</sub>/rGO nanocomposite was examined to 1415 F/g @ 1 A/g. Significant C<sub>s</sub> of MgCrO<sub>4</sub>/rGO corresponds to crystal size, increased surface area (SA) of rGO and synergistic impact produced by MgCrO<sub>4</sub> and rGO. Furthermore, energy density (44.3 Wh/kg) as well as power density (237.5 W/kg @ 1 A/g) was exhibited by nanocomposite. Additionally, collected results revealed significant effectiveness of ion transport efficiency due to small solution resistance (R<sub>s</sub> = 0.90 Ω) at MgCrO<sub>4</sub>/rGO interface. Diverse stability tests demonstrated that MgCrO<sub>4</sub>/rGO displayed stable performance over 50 h with strong structure integrity after 3000<sup>th</sup> cycles. Our outcomes demonstrate that synthesized nanohybrid exhibited remarkable electrochemical functionality and holds great potential for addressing future energy-related challenges.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"286 ","pages":"Article 117939"},"PeriodicalIF":2.6,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145927526","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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