Pub Date : 2026-03-01Epub 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":"2026-03-01","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 : 2026-03-01Epub Date: 2026-01-19DOI: 10.1016/j.poly.2026.117977
İskender Muz , Niyazi Bulut
The detection of chloroquine (CQ), a widely used antimalarial drug with emerging therapeutic roles but potential cardiotoxicity, necessitate the development of sensitive and selective biosensors. This study employs density functional theory (DFT) to systematically screen the adsorption performance and sensing potential of chloroquine on Cr-, Fe-, Mg-, Ni-, Si- and Ti-doped (ZnO)20 nanoclusters. Among all investigated dopants, the Mg-doped (ZnO)20 nanocluster exhibits the most favorable characteristics for CQ detection. It shows the highest adsorption energy (−58.11 kcal/mol), the shortest binding distance (2.10 Å) between the drug's N atom and the nanocluster's Zn site, and a significant change in dipole moment after CQ adsorption. Electronic structure analysis reveals that Mg-doping induces the most pronounced reduction in the HOMO-LUMO energy gap after CQ interaction (∼13% change), indicating enhanced charge transfer and a strong electrical signal response. The RDG and NCI analyses confirm that the adsorption is primarily governed by weak van der Waals forces (physical adsorption), the distinct electronic perturbation caused by CQ on the Mg-doped surface is notable. The results demonstrate that Mg-doped (ZnO)20 nanocluster is the most promising candidate for the development of efficient CQ biosensor.
{"title":"Enhanced chloroquine sensing on Cr, Fe, Mg, Ni, Si, and Ti-doped zinc oxide nanoclusters: A DFT study","authors":"İskender Muz , Niyazi Bulut","doi":"10.1016/j.poly.2026.117977","DOIUrl":"10.1016/j.poly.2026.117977","url":null,"abstract":"<div><div>The detection of chloroquine (CQ), a widely used antimalarial drug with emerging therapeutic roles but potential cardiotoxicity, necessitate the development of sensitive and selective biosensors. This study employs density functional theory (DFT) to systematically screen the adsorption performance and sensing potential of chloroquine on Cr-, Fe-, Mg-, Ni-, Si- and Ti-doped (ZnO)<sub>20</sub> nanoclusters. Among all investigated dopants, the Mg-doped (ZnO)<sub>20</sub> nanocluster exhibits the most favorable characteristics for CQ detection. It shows the highest adsorption energy (−58.11 kcal/mol), the shortest binding distance (2.10 Å) between the drug's N atom and the nanocluster's Zn site, and a significant change in dipole moment after CQ adsorption. Electronic structure analysis reveals that Mg-doping induces the most pronounced reduction in the HOMO-LUMO energy gap after CQ interaction (∼13% change), indicating enhanced charge transfer and a strong electrical signal response. The RDG and NCI analyses confirm that the adsorption is primarily governed by weak van der Waals forces (physical adsorption), the distinct electronic perturbation caused by CQ on the Mg-doped surface is notable. The results demonstrate that Mg-doped (ZnO)<sub>20</sub> nanocluster is the most promising candidate for the development of efficient CQ biosensor.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117977"},"PeriodicalIF":2.6,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038651","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 : 2026-03-01Epub 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":"2026-03-01","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 : 2026-03-01Epub 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":"2026-03-01","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}
Pub Date : 2026-03-01Epub Date: 2025-11-19DOI: 10.1016/j.poly.2025.117891
Michael A. Land , Mitchell J. Baker , George L. Lawless , Kai E.O. Ylijoki , Katherine N. Robertson , Jason A.C. Clyburne
The dihalopropenium salt, 1,3-dicholoro-1,3-bis(dimethylamino)propenium hexafluorophosphate, reacts with N,N-diisopropylethylamine to produce an intermediate halopropyne iminium cation. This transient intermediate reacts with diphenylamine to produce a tetraamino propenium salt, 1,3-bis(dimethylamino)-1,3-bis(diphenylamino)propenium hexafluorophosphate. In contrast, reaction with diphenylphosphine under similar conditions produces a putative dicationic four-membered phosphacycle, which subsequently adds a fluoride ion to give the stable isolable salt, 1-fluoro-1,1-diphenyl-2,4-bis(dimethylamino)phosphetenium hexafluorophosphate. Both compounds have been fully characterized including X-ray crystal structures. Reasons for the different observed reactivities are discussed.
{"title":"Contrasting the reactions of diphenylamine and diphenylphosphine with the 1,3-dicholoro-1,3-bis(dimethylamino)propenium ion","authors":"Michael A. Land , Mitchell J. Baker , George L. Lawless , Kai E.O. Ylijoki , Katherine N. Robertson , Jason A.C. Clyburne","doi":"10.1016/j.poly.2025.117891","DOIUrl":"10.1016/j.poly.2025.117891","url":null,"abstract":"<div><div>The dihalopropenium salt, 1,3-dicholoro-1,3-<em>bis</em>(dimethylamino)propenium hexafluorophosphate, reacts with <em>N</em>,<em>N</em>-diisopropylethylamine to produce an intermediate halopropyne iminium cation. This transient intermediate reacts with diphenylamine to produce a tetraamino propenium salt, 1,3-<em>bis</em>(dimethylamino)-1,3-<em>bis</em>(diphenylamino)propenium hexafluorophosphate. In contrast, reaction with diphenylphosphine under similar conditions produces a putative dicationic four-membered phosphacycle, which subsequently adds a fluoride ion to give the stable isolable salt, 1-fluoro-1,1-diphenyl-2,4-<em>bis</em>(dimethylamino)phosphetenium hexafluorophosphate. Both compounds have been fully characterized including X-ray crystal structures. Reasons for the different observed reactivities are discussed.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117891"},"PeriodicalIF":2.6,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145929093","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}
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":"2026-03-01","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 : 2026-03-01Epub 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":"2026-03-01","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 : 2026-03-01Epub 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":"2026-03-01","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 : 2026-03-01Epub Date: 2026-01-19DOI: 10.1016/j.poly.2026.117978
Louchachha Isam , Faris Abdelmajid , Khaldoune Khadija , Rafya Meriem , Edder Youssef , Boualy Brahim , Rachid Hsissou , Ait Ali Mustapha , Karim Abdallah
Functionalized sesquiterpenes are a highly sought-after compounds for their olfactive as well as therapeutic properties. Herein, we report the oxidation of γ-dehydro-arylhimachalene, an olefin obtained via the aromatization of himachalene mixture, the major components of cadar oil, using ruthenium- and vanadium-based catalysts. While ruthenium catalyzed oxidation leads to the formation of a ketone and an aldehyde with poor selectivity, vanadium-catalyzed oxidation of the same substrate using hydrogen peroxide as an oxidant leads to the selective formation of the ketone. Finally, γ-dehydro-arylhimachalene, the ketone and the aldehyde were explored as antibacterial agents against two gram positive (Staphylococcus Aureus and Enterococcus faecalis) and two gram negative (Escherechia Coli and Pseudomonas aeruginosa) bacteria. The ketone showed the best activity against E.coli and P. aeruginosa with MIC equal to 0.78 mg/mL and 0.1 mg/mL respectively, while γ-dehydro-arylhimachalene displayed the best activity, with MIC equal to 1.56 and 0.2 mg/mL against S.aureus and E. faecalis respectively.
{"title":"Catalytic oxidation of γ-dehydro-arylhimachalene: synthesis and antibacterial study of novel oxygenated derivatives of himachalanes","authors":"Louchachha Isam , Faris Abdelmajid , Khaldoune Khadija , Rafya Meriem , Edder Youssef , Boualy Brahim , Rachid Hsissou , Ait Ali Mustapha , Karim Abdallah","doi":"10.1016/j.poly.2026.117978","DOIUrl":"10.1016/j.poly.2026.117978","url":null,"abstract":"<div><div>Functionalized sesquiterpenes are a highly sought-after compounds for their olfactive as well as therapeutic properties. Herein, we report the oxidation of γ-dehydro-arylhimachalene, an olefin obtained via the aromatization of himachalene mixture, the major components of cadar oil, using ruthenium- and vanadium-based catalysts. While ruthenium catalyzed oxidation leads to the formation of a ketone and an aldehyde with poor selectivity, vanadium-catalyzed oxidation of the same substrate using hydrogen peroxide as an oxidant leads to the selective formation of the ketone. Finally, γ-dehydro-arylhimachalene, the ketone and the aldehyde were explored as antibacterial agents against two gram positive (<em>Staphylococcus Aureus</em> and <em>Enterococcus faecalis)</em> and two gram negative (<em>Escherechia Coli</em> and <em>Pseudomonas aeruginosa)</em> bacteria<em>.</em> The ketone showed the best activity against <em>E.coli</em> and <em>P. aeruginosa</em> with MIC equal to 0.78 mg/mL and 0.1 mg/mL respectively, while γ-dehydro-arylhimachalene displayed the best activity, with MIC equal to 1.56 and 0.2 mg/mL against S.aureus and <em>E. faecalis</em> respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117978"},"PeriodicalIF":2.6,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038652","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 : 2026-03-01Epub 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":"2026-03-01","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}
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