Rhenium(I) tricarbonyl complexes with 2,6-bis(pyrazol-1-yl)pyridine ligands functionalized with COOH, COOCH3, and NH2 were synthesized via UV-induced substitution of Re(CO)5Br in acetone under 365 nm irradiation. Single-crystal X-ray diffraction revealed distorted octahedral geometries, with ReN bond lengths of 2.133–2.239 Å, NReN angles of 73.30–73.98°, and ReBr distances of 2.627–2.642 Å, reflecting the influence of ligand substituents. ATR-IR spectroscopy demonstrated that electron-withdrawing COOH and COOCH3 groups caused slight blue shifts in ν(CO), whereas NH2 induced red shifts, consistent with modulation of metal-to-ligand backbonding. UV–Vis studies showed that acetone preserved complex stability, whereas acetonitrile caused significant destabilization. Variable-temperature 1H/13C NMR confirmed stable bidentate coordination in solution. DFT calculations revealed that electron-withdrawing groups lowered LUMO energies, while electron-donating group raised HOMO levels, tuning charge-transfer behavior. ESI-MS and elemental analyses confirmed molecular purity. These results indicate that functionalization of ligands enables precise control over rhenium(I) structural and electronic properties.
{"title":"Synthesis and structural characterization of rhenium(I) tricarbonyl complexes with 2,6-bis(pyrazol-1-yl)pyridine ligands functionalized with carboxyl (COOH), methoxycarbonyl (COOCH3), and amino (NH2) groups","authors":"Natcha Temnuch , Thinnaphat Poonsawat , Thitiwat Tanyalax , Peerapong Chumkaeo , Teera Chantarojsiri , Khetpakorn Chakarawet , Yumi Yakiyama , Hidehiro Sakurai , Ekasith Somsook","doi":"10.1016/j.poly.2026.117971","DOIUrl":"10.1016/j.poly.2026.117971","url":null,"abstract":"<div><div>Rhenium(I) tricarbonyl complexes with 2,6-bis(pyrazol-1-yl)pyridine ligands functionalized with <img>COOH, <img>COOCH<sub>3</sub>, and <img>NH<sub>2</sub> were synthesized <em>via</em> UV-induced substitution of Re(CO)<sub>5</sub>Br in acetone under 365 nm irradiation. Single-crystal X-ray diffraction revealed distorted octahedral geometries, with Re<img>N bond lengths of 2.133–2.239 Å, N<img>Re<img>N angles of 73.30–73.98°, and Re<img>Br distances of 2.627–2.642 Å, reflecting the influence of ligand substituents. ATR-IR spectroscopy demonstrated that electron-withdrawing <img>COOH and <img>COOCH<sub>3</sub> groups caused slight blue shifts in <em>ν</em>(CO), whereas <img>NH<sub>2</sub> induced red shifts, consistent with modulation of metal-to-ligand backbonding. UV–Vis studies showed that acetone preserved complex stability, whereas acetonitrile caused significant destabilization. Variable-temperature <sup>1</sup>H/<sup>13</sup>C NMR confirmed stable bidentate coordination in solution. DFT calculations revealed that electron-withdrawing groups lowered LUMO energies, while electron-donating group raised HOMO levels, tuning charge-transfer behavior. ESI-MS and elemental analyses confirmed molecular purity. These results indicate that functionalization of ligands enables precise control over rhenium(I) structural and electronic properties.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117971"},"PeriodicalIF":2.6,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038653","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.poly.2026.117972
Samantha E. Bodman , Ezra D.G. Prattley , Christopher M. Fitchett
The reaction of 9,10-bis(2-pyridyl)anthracene (1) with silver and copper(I) salts gave a range of networks; Ag213(BF4)2 (3), Cu213(BF4)2 (4), Ag213(PF6)2 (5), with non-coordinating anions, along with a discrete complex Ag21(CH3CN)4(OTf)2 (6) and polymers Ag1NO3 (7) and Cu21I2 (8) with coordinating anions. All formed with an approximately perpendicular conformation of the pyridine rings relative to the anthracene core, which directs the metal, along with its associated ligands, over the π-face of anthracene blocking intermolecular π–π face-to-face interactions. All the complexes exhibited blue-green florescence in the solid-state that was very similar to that of 1 in the solution state.
{"title":"The structural regulation and photoluminescence of the silver and copper(I) complexes of 9,10-bis(2-pyridyl)anthracene","authors":"Samantha E. Bodman , Ezra D.G. Prattley , Christopher M. Fitchett","doi":"10.1016/j.poly.2026.117972","DOIUrl":"10.1016/j.poly.2026.117972","url":null,"abstract":"<div><div>The reaction of 9,10-bis(2-pyridyl)anthracene (<strong>1</strong>) with silver and copper(I) salts gave a range of networks; Ag<sub>2</sub><strong>1</strong><sub>3</sub>(BF<sub>4</sub>)<sub>2</sub> (<strong>3</strong>), Cu<sub>2</sub><strong>1</strong><sub>3</sub>(BF<sub>4</sub>)<sub>2</sub> (<strong>4</strong>), Ag<sub>2</sub><strong>1</strong><sub>3</sub>(PF<sub>6</sub>)<sub>2</sub> (<strong>5</strong>), with non-coordinating anions, along with a discrete complex Ag<sub>2</sub><strong>1</strong>(CH<sub>3</sub>CN)<sub>4</sub>(OTf)<sub>2</sub> (<strong>6</strong>) and polymers Ag<strong>1</strong>NO<sub>3</sub> (<strong>7</strong>) and Cu<sub>2</sub><strong>1</strong>I<sub>2</sub> (<strong>8</strong>) with coordinating anions. All formed with an approximately perpendicular conformation of the pyridine rings relative to the anthracene core, which directs the metal, along with its associated ligands, over the π-face of anthracene blocking intermolecular π–π face-to-face interactions. All the complexes exhibited blue-green florescence in the solid-state that was very similar to that of <strong>1</strong> in the solution state.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117972"},"PeriodicalIF":2.6,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038654","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.poly.2026.117973
Tamer H.A. Hasanin , Muhrail E.S. Aziz , Mohamed Y. El-Sayed , I.M. Ahmed , Mohammad F.H. Alruwalli , Amna H.M. Mahmoud , Mahmoud A.A. Ibrahim
In this study, the sensing potentiality of the pristine and Pt-doped RuC nanosheets toward small organic molecules—urea (UR) and thiourea (TU)—was examined using density functional theory methods. The adsorption process of UR and TU molecules was simulated in vertical and parallel orientations relative to the pristine and Pt-doped RuC nanosheets. Energetically, the examined 2D nanosheets exhibited commendable sensing capabilities toward the UR and TU molecules in both orientations, with adsorption energies reaching −26.85 and −42.96 kcal/mol, respectively. Bader charge analysis revealed that both pristine and Pt-doped RuC nanosheets acted as electron donors during the adsorption process of UR and TU molecules, as indicated by the charge transfer values. Alterations in the energy gap values of the pristine and Pt-doped RuC nanosheets were observed following UR and TU adsorption, verifying the occurrence of the adsorption process. The recovery time (τ) analysis revealed that the desorption of the UR molecule from both 2D nanosheets was faster than that of the TU molecule, with τ values of 4.50 × 107 and 2.17 × 1019 s for UR⋯ and TU⋯Pt-doped RuC complexes at 298.15 K, respectively. The density of states plots showed additional peaks upon UR and TU adsorption on the investigated RuC-based nanosheets. These results highlight the potential of the RuC-based nanosheets as efficient sensors for UR and TU molecules.
{"title":"Pristine and Pt-doped RuC nanosheets as urea and thiourea sensors: DFT-based insights","authors":"Tamer H.A. Hasanin , Muhrail E.S. Aziz , Mohamed Y. El-Sayed , I.M. Ahmed , Mohammad F.H. Alruwalli , Amna H.M. Mahmoud , Mahmoud A.A. Ibrahim","doi":"10.1016/j.poly.2026.117973","DOIUrl":"10.1016/j.poly.2026.117973","url":null,"abstract":"<div><div>In this study, the sensing potentiality of the pristine and Pt-doped RuC nanosheets toward small organic molecules—urea (UR) and thiourea (TU)—was examined using density functional theory methods. The adsorption process of UR and TU molecules was simulated in vertical and parallel orientations relative to the pristine and Pt-doped RuC nanosheets. Energetically, the examined 2D nanosheets exhibited commendable sensing capabilities toward the UR and TU molecules in both orientations, with adsorption energies reaching −26.85 and −42.96 kcal/mol, respectively. Bader charge analysis revealed that both pristine and Pt-doped RuC nanosheets acted as electron donors during the adsorption process of UR and TU molecules, as indicated by the charge transfer values. Alterations in the energy gap values of the pristine and Pt-doped RuC nanosheets were observed following UR and TU adsorption, verifying the occurrence of the adsorption process. The recovery time (<em>τ</em>) analysis revealed that the desorption of the UR molecule from both 2D nanosheets was faster than that of the TU molecule, with <em>τ</em> values of 4.50 × 10<sup>7</sup> and 2.17 × 10<sup>19</sup> s for UR⋯ and TU⋯Pt-doped RuC complexes at 298.15 K, respectively. The density of states plots showed additional peaks upon UR and TU adsorption on the investigated RuC-based nanosheets. These results highlight the potential of the RuC-based nanosheets as efficient sensors for UR and TU molecules.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117973"},"PeriodicalIF":2.6,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146039332","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.poly.2026.117963
Aurélie M.K. Kuisseu , Bridget N. Ndosiri , Aminou Mohamadou , Ledoux S. Pouamo , Colince Nde , Frédéric Capet , Michel Foulon , Mohammad Azam , Justin Nenwa
Two copper(II) coordination polymers bridged by dicyanamido (N(CN)2−)- and azido (N3−) ligands, [CuLN(CN)2]n (1) and [{CuLN3}2(H2O)]n (2) (L− = N-(2-pyridylmethyl)-L-alaninato) have been synthesized and thoroughly studied using structural and spectroscopic methods. Both complexes crystallize in the chiral orthorhombic P212121 space group. Complex 1 features 1D zigzag chains through the two terminal nitrogen nitrile groups of the μ1,5-bridging N(CN)2− ligand. These chains are assembled via intermolecular N–H···O hydrogen bonding interactions, forming a 3D supramolecular network. Complex 2 is a dissymmetric dimer with the Cu1 center being in a distorted square pyramidal geometry environment, while the Cu2 center is in a distorted octahedral geometry. In complex 2, an infinite 3D supramolecular structure is achieved via Cu1-O2i bonds, O2i being the oxygen atom of a carboxylate group from the L− ligand of an adjacent dimer. Intermolecular hydrogen bonding interactions of the type N–H···O in 1 and N–H···O and O–H···O in 2 contribute to stabilizing the three-dimensional frameworks. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint (2D-FP) plots reveal that the two structures are dominated by the H┄H and N⋯H/H⋯N contacts. Upon excitation at 315 nm, maximum emissions centered at 498 nm and 805 nm for 1 and at 497 nm and 805 nm for 2 are exhibited. These luminescence behaviors are attributed to charge transition between the L− ligand and the Cu2+ ions.
{"title":"Two dicyanamido- and azido-bridged Cu(II) coordination polymers with N-(2-pyridylmethyl)-L-alaninato as chiral ligand: Synthesis, structures, luminescence properties, and Hirshfeld surface analysis","authors":"Aurélie M.K. Kuisseu , Bridget N. Ndosiri , Aminou Mohamadou , Ledoux S. Pouamo , Colince Nde , Frédéric Capet , Michel Foulon , Mohammad Azam , Justin Nenwa","doi":"10.1016/j.poly.2026.117963","DOIUrl":"10.1016/j.poly.2026.117963","url":null,"abstract":"<div><div>Two copper(II) coordination polymers bridged by dicyanamido (N(CN)<sub>2</sub><sup>−</sup>)- and azido (N<sub>3</sub><sup>−</sup>) ligands, [CuLN(CN)<sub>2</sub>]<sub>n</sub> (<strong>1</strong>) and [{CuLN<sub>3</sub>}<sub>2</sub>(H<sub>2</sub>O)]<sub>n</sub> (<strong>2</strong>) (L<sup>−</sup> = N-(2-pyridylmethyl)-L-alaninato) have been synthesized and thoroughly studied using structural and spectroscopic methods. Both complexes crystallize in the chiral orthorhombic <em>P</em>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> space group. Complex <strong>1</strong> features 1D zigzag chains through the two terminal nitrogen nitrile groups of the <em>μ</em><sub>1,5</sub>-bridging N(CN)<sub>2</sub><sup>−</sup> ligand. These chains are assembled <em>via</em> intermolecular N–H···O hydrogen bonding interactions, forming a 3D supramolecular network. Complex <strong>2</strong> is a dissymmetric dimer with the Cu1 center being in a distorted square pyramidal geometry environment, while the Cu2 center is in a distorted octahedral geometry. In complex <strong>2</strong>, an infinite 3D supramolecular structure is achieved <em>via</em> Cu1-O2<sup>i</sup> bonds, O2<sup>i</sup> being the oxygen atom of a carboxylate group from the L<sup>−</sup> ligand of an adjacent dimer. Intermolecular hydrogen bonding interactions of the type N–H···O in <strong>1</strong> and N–H···O and O–H···O in <strong>2</strong> contribute to stabilizing the three-dimensional frameworks. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint (2D-FP) plots reveal that the two structures are dominated by the H┄H and N⋯H/H⋯N contacts. Upon excitation at 315 nm, maximum emissions centered at 498 nm and 805 nm for <strong>1</strong> and at 497 nm and 805 nm for <strong>2</strong> are exhibited. These luminescence behaviors are attributed to charge transition between the L<sup>−</sup> ligand and the Cu<sup>2+</sup> ions.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117963"},"PeriodicalIF":2.6,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038650","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 : 2026-01-12DOI: 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}
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