Pub Date : 2026-02-01Epub Date: 2025-11-28DOI: 10.1016/j.poly.2025.117905
Qing-Dou Xu , Yu-Jing Ma , Han Xiao , Qian-Qian Yang , Min Cao , Jun-Jie Xu
To investigate the influence of the electron donating ability of the sensitization ligand on the photoluminescence properties in Sm(III) and Ce(III) complexes, a group of complexes [Sm(NO3)3(4,4′-dmbpy)2] (1) and [Ce(NO3)3(4,4′-dmbpy)2] (2) (4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized and fully characterized. Comparing the photoluminescence properties of complexes 1 and [Sm(NO3)3(bpy)2] or 2 and [Ce(NO3)3(bpy)2], the experimental results show that for Sm(III) complexes, decreasing the electron donating ability of the sensitization ligand leads to an increase in the maximum emission band intensity and fluorescence lifetime; for Ce(III) complexes, weakening the electron donating ability of the sensitization ligand results in a decrease in the maximum emission band intensity and fluorescence lifetime.
{"title":"Opposing effects of bipyridine ligand substitution on the luminescence of Sm(III) (f-f) and Ce(III) (d-f) complexes","authors":"Qing-Dou Xu , Yu-Jing Ma , Han Xiao , Qian-Qian Yang , Min Cao , Jun-Jie Xu","doi":"10.1016/j.poly.2025.117905","DOIUrl":"10.1016/j.poly.2025.117905","url":null,"abstract":"<div><div>To investigate the influence of the electron donating ability of the sensitization ligand on the photoluminescence properties in Sm(III) and Ce(III) complexes, a group of complexes [Sm(NO<sub>3</sub>)<sub>3</sub>(4,4′-dmbpy)<sub>2</sub>] (<strong>1</strong>) and [Ce(NO<sub>3</sub>)<sub>3</sub>(4,4′-dmbpy)<sub>2</sub>] (<strong>2</strong>) (4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized and fully characterized. Comparing the photoluminescence properties of complexes <strong>1</strong> and [Sm(NO<sub>3</sub>)<sub>3</sub>(bpy)<sub>2</sub>] or <strong>2</strong> and [Ce(NO<sub>3</sub>)<sub>3</sub>(bpy)<sub>2</sub>], the experimental results show that for Sm(III) complexes, decreasing the electron donating ability of the sensitization ligand leads to an increase in the maximum emission band intensity and fluorescence lifetime; for Ce(III) complexes, weakening the electron donating ability of the sensitization ligand results in a decrease in the maximum emission band intensity and fluorescence lifetime.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117905"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693376","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 : 2026-02-01Epub Date: 2025-12-11DOI: 10.1016/j.poly.2025.117932
Kamal Krishna Dutta , Mridul Boro , Rosa M. Gomila , Antonio Frontera , Miquel Barcelo-Oliver , Munmi Gogoi , Akalesh Kumar Verma , Manjit K. Bhattacharyya
Two new Zn(II) metal-organic compounds of 3-Aminopyridine and 1,10-phenanthroline ligand viz. [Zn(phen)2Cl][Zn(3-Ampy)Cl3] (1) and [Zn(3-Ampy)2Cl2] (2) (where, 3-Ampy = 3-Aminopyridine, phen = 1,10-phenanthroline) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction technique. Crystal structure analysis of the compounds reveal the formation of supramolecular layered architecture in 1 aided by CH⋯Cl, NH⋯Cl, NH⋯N hydrogen bonding interactions along with aromatic π-stacking, CH⋯π and anion(Cl)⋯π interactions. Intriguing anion–π/π–π/anion–π assemblies found in compound 1 have provided further rigidity to the crystal structure. The interesting aspect of compound 2 is the formation of a supramolecular synthon via strong directional NH⋯Cl hydrogen bonds and auxiliary CH⋯Cl and π-stacking interactions. These non-covalent interactions helping in the formation of anion–π/π–π/anion–π assemblies in compound 1 and supramolecular synthon in compound 2 have been further studied theoretically using density functional theory (DFT) calculations, non-covalent interaction (NCI) plot index, quantum theory of atoms in molecules (QTAIM) and molecular electrostatic potential (MEP) surface analysis. The in vitro cytotoxicity of the compounds through Trypan blue exclusion and apoptosis assays showcase their selective cytotoxic potential toward the Dalton's Lymphoma cancer cell line while sparing healthy PBMC cells. To explore the structure–activity relationship, molecular docking was conducted to understand the binding behavior of the synthesized compounds with target cancer-related receptors.
{"title":"Supramolecular assemblies in Zn(II) metal-organic compounds involving 3-aminopyridine and 1,10-phenanthroline: antiproliferative evaluation and theoretical studies","authors":"Kamal Krishna Dutta , Mridul Boro , Rosa M. Gomila , Antonio Frontera , Miquel Barcelo-Oliver , Munmi Gogoi , Akalesh Kumar Verma , Manjit K. Bhattacharyya","doi":"10.1016/j.poly.2025.117932","DOIUrl":"10.1016/j.poly.2025.117932","url":null,"abstract":"<div><div>Two new Zn(II) metal-organic compounds of 3-Aminopyridine and 1,10-phenanthroline ligand viz. [Zn(phen)<sub>2</sub>Cl][Zn(3-Ampy)Cl<sub>3</sub>] (<strong>1</strong>) and [Zn(3-Ampy)<sub>2</sub>Cl<sub>2</sub>] (<strong>2</strong>) (where, 3-Ampy = 3-Aminopyridine, phen = 1,10-phenanthroline) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction technique. Crystal structure analysis of the compounds reveal the formation of supramolecular layered architecture in <strong>1</strong> aided by C<img>H⋯Cl, N<img>H⋯Cl, N<img>H⋯N hydrogen bonding interactions along with aromatic π-stacking, C<img>H⋯π and anion(Cl)⋯π interactions. Intriguing anion–π/π–π/anion–π assemblies found in compound <strong>1</strong> have provided further rigidity to the crystal structure. The interesting aspect of compound <strong>2</strong> is the formation of a supramolecular <span><math><msubsup><mi>R</mi><mn>4</mn><mn>4</mn></msubsup><mfenced><mn>8</mn></mfenced></math></span> synthon via strong directional N<img>H⋯Cl hydrogen bonds and auxiliary C<img>H⋯Cl and π-stacking interactions. These non-covalent interactions helping in the formation of anion–π/π–π/anion–π assemblies in compound <strong>1</strong> and supramolecular <span><math><msubsup><mi>R</mi><mn>4</mn><mn>4</mn></msubsup><mfenced><mn>8</mn></mfenced></math></span> synthon in compound <strong>2</strong> have been further studied theoretically using density functional theory (DFT) calculations, non-covalent interaction (NCI) plot index, quantum theory of atoms in molecules (QTAIM) and molecular electrostatic potential (MEP) surface analysis. The in vitro cytotoxicity of the compounds through Trypan blue exclusion and apoptosis assays showcase their selective cytotoxic potential toward the Dalton's Lymphoma cancer cell line while sparing healthy PBMC cells. To explore the structure–activity relationship, molecular docking was conducted to understand the binding behavior of the synthesized compounds with target cancer-related receptors.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117932"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797921","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 : 2026-02-01Epub Date: 2025-11-17DOI: 10.1016/j.poly.2025.117870
Fawad Khan , Muhammad Ilyas , Muhammad Idrees , Abida Iqbal , Mah Noor , Majed M. Alghamdi , Adel A. El-Zahhar , Syed Zuhair Abbas Shah , Sana Ullah Asif
In search of efficient thermoelectric (TE) materials to utilize waste heat and convert it to electrical energy, we modeled penta-atomic XMoGeP2 (X = S, Se) monolayers for thermoelectric applications. DFT-based study is carried out to find the optimized structures. Cohesive energies per unit atom and phonon calculations confirm the stabilities of these monolayers. Thermal stability of these monolayers is confirmed at 300 K using AIMD simulations. The electronic properties confirm an indirect band gap semi-conducting nature in these monolayers. The band gap increase/decrease is detected with compressional/tensile strains. The optical behavior reveals that these monolayers are optically active in the visible light range in strain-free environment which makes them suitable for optoelectronic devices. Effect of strain is also observed on the optical properties, which makes these materials suitable to interact with infrared light when subjected to tensile strain. Boltzmann's transport theory is utilized to predict the thermoelectric response of these monolayers, which reveals that SeMoGeP2 has greater ZT values than SMoGeP2.
{"title":"Computational insights into strain-induced structural, electronic, optical and thermoelectric properties of XMoGeP2 (X = S, Se) monolayers","authors":"Fawad Khan , Muhammad Ilyas , Muhammad Idrees , Abida Iqbal , Mah Noor , Majed M. Alghamdi , Adel A. El-Zahhar , Syed Zuhair Abbas Shah , Sana Ullah Asif","doi":"10.1016/j.poly.2025.117870","DOIUrl":"10.1016/j.poly.2025.117870","url":null,"abstract":"<div><div>In search of efficient thermoelectric (TE) materials to utilize waste heat and convert it to electrical energy, we modeled penta-atomic XMoGeP<sub>2</sub> (X = S, Se) monolayers for thermoelectric applications. DFT-based study is carried out to find the optimized structures. Cohesive energies per unit atom and phonon calculations confirm the stabilities of these monolayers. Thermal stability of these monolayers is confirmed at 300 K using AIMD simulations. The electronic properties confirm an indirect band gap semi-conducting nature in these monolayers. The band gap increase/decrease is detected with compressional/tensile strains. The optical behavior reveals that these monolayers are optically active in the visible light range in strain-free environment which makes them suitable for optoelectronic devices. Effect of strain is also observed on the optical properties, which makes these materials suitable to interact with infrared light when subjected to tensile strain. Boltzmann's transport theory is utilized to predict the thermoelectric response of these monolayers, which reveals that SeMoGeP<sub>2</sub> has greater ZT values than SMoGeP<sub>2</sub>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117870"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577691","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 : 2026-02-01Epub Date: 2025-10-29DOI: 10.1016/j.poly.2025.117866
David A. Wink , Leandro L. Coutinho , Robert Y.S. Cheng , Lisa A. Ridnour , Jon Fukuto
The recognition of nitric oxide and nitrogen oxides as key elements in human biology has driven the development of one of the most extensive areas of research in recent decades, consistently uncovering new insights into therapy and disease. These molecules are central to redox biology, with their inorganic chemistry playing a significant role in many biological systems. This review explores how fundamental chemical properties, kinetics, and thermodynamics influence important biological outcomes, including cancer, covering both normal physiology and disease states. The distinct chemical traits of these compounds allow for precise regulation of biological processes. Emerging concepts in cancer and other diseases will be discussed to highlight innovative treatments for advanced-stage conditions.
{"title":"Fundamental inorganic chemistry and cancer and inflammatory mechanism of NO. kinetic approach to revealing insights into Cancer and other diseases","authors":"David A. Wink , Leandro L. Coutinho , Robert Y.S. Cheng , Lisa A. Ridnour , Jon Fukuto","doi":"10.1016/j.poly.2025.117866","DOIUrl":"10.1016/j.poly.2025.117866","url":null,"abstract":"<div><div>The recognition of nitric oxide and nitrogen oxides as key elements in human biology has driven the development of one of the most extensive areas of research in recent decades, consistently uncovering new insights into therapy and disease. These molecules are central to redox biology, with their inorganic chemistry playing a significant role in many biological systems. This review explores how fundamental chemical properties, kinetics, and thermodynamics influence important biological outcomes, including cancer, covering both normal physiology and disease states. The distinct chemical traits of these compounds allow for precise regulation of biological processes. Emerging concepts in cancer and other diseases will be discussed to highlight innovative treatments for advanced-stage conditions.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117866"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577750","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}
Co-crystallization is one beneficial method to synthesize a single crystal from two different molecules, providing high ionic charges. Recently, we successfully synthesized several hybrid complexes between a 12-nuclear cationic framework of {AuI6AgI3CuII3(tdme)2(D-pen)6}3+ (tdme = 1,1,1-tris(diphenylphosphinomethyl)ethane); D-pen2− = D-penicilaminate) and a 5-nuclear anionic molecule of [MI3CoIII2(pen)6]3− (M = Au or Ag) through a slow evaporation process. X-ray and spectroscopic analysis revealed that the cationic framework has selective chiral recognition towards one orientation of the penicillamine ligand in the anionic complex. Several factors, such as ionic interaction, solubility of substrates, and suitable cavity space of the {AuI6AgI3CuII3(tdme)2(D-pen)6}3+ framework, play a role in crystallizing hybrid complexes from the reaction mixture.
{"title":"Selective co-crystallization of [AuI6AgI3CuII3]3+ and [MI3CoIII2]3− (M = Au/Ag) complexes containing penicillamine ligand","authors":"Benny Wahyudianto , Tatsuhiro Kojima , Nobuto Yoshinari , Takumi Konno","doi":"10.1016/j.poly.2025.117821","DOIUrl":"10.1016/j.poly.2025.117821","url":null,"abstract":"<div><div>Co-crystallization is one beneficial method to synthesize a single crystal from two different molecules, providing high ionic charges. Recently, we successfully synthesized several hybrid complexes between a 12-nuclear cationic framework of {Au<sup>I</sup><sub>6</sub>Ag<sup>I</sup><sub>3</sub>Cu<sup>II</sup><sub>3</sub>(tdme)<sub>2</sub>(D-pen)<sub>6</sub>}<sup>3+</sup> (tdme = 1,1,1-tris(diphenylphosphinomethyl)ethane); D-pen<sup>2−</sup> = D-penicilaminate) and a 5-nuclear anionic molecule of [M<sup>I</sup><sub>3</sub>Co<sup>III</sup><sub>2</sub>(pen)<sub>6</sub>]<sup>3−</sup> (M = Au or Ag) through a slow evaporation process. X-ray and spectroscopic analysis revealed that the cationic framework has selective chiral recognition towards one orientation of the penicillamine ligand in the anionic complex. Several factors, such as ionic interaction, solubility of substrates, and suitable cavity space of the {Au<sup>I</sup><sub>6</sub>Ag<sup>I</sup><sub>3</sub>Cu<sup>II</sup><sub>3</sub>(tdme)<sub>2</sub>(D-pen)<sub>6</sub>}<sup>3+</sup> framework, play a role in crystallizing hybrid complexes from the reaction mixture.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117821"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322556","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 : 2026-01-01Epub Date: 2025-10-30DOI: 10.1016/j.poly.2025.117867
Nan Xu , Emily Suchta , Michael J. Shaw , Gadden Lych , Navamoney Arulsamy , Sela Cameron , Joshua Bueno
Nitrosonaphthols belong to the class of C-nitroso compounds, having an additional hydroxyl group on the naphthalene ring. Their coordination chemistry is rich due to the presence of both nitroso and hydroxyl groups. Despite the various binding modes of nitrosonaphthols in metal complexes, their interactions with heme model complexes remain unexplored. In this work, we report the synthesis and characterization of a six-coordinate ruthenium nitrosyl porphyrin complex, (OEP)Ru(NO)(η1-ONC10H6O) from the reaction of excess 2-nitroso-1-naphthol with the nitrosyl ruthenium alkoxide precursor, (OEP)Ru(NO)(O-i-C5H11) (OEP = 2,3,7,8,12,13,17,18-octaethylporphinato dianion). The complex was characterized by various methods, including 1D and 2D NMR spectroscopy (COSY, HSQC, HMBC, and 1D-NOE), IR spectroscopy, and single-crystal X-ray crystallography. The molecular structure of (OEP)Ru(NO)(η1-ONC10H6O) reveals monodentate O-binding to the metal through the nitroso oxygen atom of the oxo-oxime tautomer. The intermolecular interactions within the crystalline packing of the complex were investigated using Hirshfeld surface analysis. In addition, the redox behavior of (OEP)Ru(NO)(η1-ONC10H6O) was studied through cyclic voltammetry in CH2Cl2. As far as we know, the structure of (OEP)Ru(NO)(η1-ONC10H6O) represents the first member of the class of monodentate 1,2-nitrosonaphthol metal complexes.
{"title":"Synthesis, solid state molecular structure, and cyclic voltammetry of a ruthenium nitrosyl porphyrin with a nitrosonaphthol ligand","authors":"Nan Xu , Emily Suchta , Michael J. Shaw , Gadden Lych , Navamoney Arulsamy , Sela Cameron , Joshua Bueno","doi":"10.1016/j.poly.2025.117867","DOIUrl":"10.1016/j.poly.2025.117867","url":null,"abstract":"<div><div>Nitrosonaphthols belong to the class of <em>C</em>-nitroso compounds, having an additional hydroxyl group on the naphthalene ring. Their coordination chemistry is rich due to the presence of both nitroso and hydroxyl groups. Despite the various binding modes of nitrosonaphthols in metal complexes, their interactions with heme model complexes remain unexplored. In this work, we report the synthesis and characterization of a six-coordinate ruthenium nitrosyl porphyrin complex, (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) from the reaction of excess 2-nitroso-1-naphthol with the nitrosyl ruthenium alkoxide precursor, (OEP)Ru(NO)(O-<em>i</em>-C<sub>5</sub>H<sub>11</sub>) (OEP = 2,3,7,8,12,13,17,18-octaethylporphinato dianion). The complex was characterized by various methods, including 1D and 2D NMR spectroscopy (COSY, HSQC, HMBC, and 1D-NOE), IR spectroscopy, and single-crystal X-ray crystallography. The molecular structure of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) reveals monodentate <em>O</em>-binding to the metal through the nitroso oxygen atom of the oxo-oxime tautomer. The intermolecular interactions within the crystalline packing of the complex were investigated using Hirshfeld surface analysis. In addition, the redox behavior of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) was studied through cyclic voltammetry in CH<sub>2</sub>Cl<sub>2</sub>. As far as we know, the structure of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) represents the first member of the class of monodentate 1,2-nitrosonaphthol metal complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117867"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467044","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}
Several biological activities such as antioxidant, antibacterial, and DNA binding of ruthenium, iridium, and rhodium complexes of a phosphinite were investigated. For this purpose, firstly, a new amide was synthesized from the reaction of 2-(phenylthio)aniline with DL-mandelic acid in a solvent-free environment using microwave irradiation. Subsequently, this amide was converted to its phosphinite counterpart. Then, Ru(II), Ir(III), and Rh(I) complexes (3–6) of the phosphinite were synthesized and characterized by several techniques such as microanalysis, IR, and NMR spectroscopy, and in the case of 4 by single crystal X-ray crystallography. Finally, antioxidant, antimicrobial, and DNA binding activities of [C20H16NOS{OPPh2-Ru(ηBergamini et al. (2004)6-p-cymene)Cl2}] (3), [C20H16NOS{OPPh2-Ru(ηBergamini et al. (2004)6-benzene)Cl2}] (4), [C20H16NOS{OPPh2-Ir(ηGaw et al. (2002)5-C5Me5)Cl2}] (5), and [C20H16NOS{OPPh2-Rh(cod)Cl}] (6) complexes were tested. To determine antioxidant activities of the complexes, DPPH (2,2-diphenyl-1-picryl hydrazyl) free radical scavenging, metal chelation, and reducing power activities were measured. At 200.0 mgL−1 concentration, complex 4 showed the highest radical scavenging (74.53 ± 1.76 %) and metal chelating activity (63.91 ± 1.54 %), while complex 3 exhibited the highest reducing power activity. Antibacterial activity of the compounds was determined with four pathogenic bacteria. Only ruthenium complexes 3 and 4 had weak activity against two Gram-positive bacteria, while the other complexes (5 and 6) did not show any antibacterial activity. Electrophoresis results using calf thymus DNA (CT-DNA) displayed that all complexes had DNA binding activity at different rates.
研究了一种亚磷酸盐的钌、铱、铑配合物的抗氧化、抗菌和DNA结合等生物活性。为此，首先在无溶剂环境下，利用微波辐射，由2-（苯基硫代）苯胺与dl -扁桃酸反应合成了一种新的酰胺。随后，这种酰胺被转化为它的亚磷酸盐对应物。然后，合成了亚磷酸盐的Ru(II), Ir（III）和Rh(I)配合物（3-6），并通过微量分析，Ir和NMR等多种技术进行了表征，对4进行了单晶x射线晶体学表征。最后，测试了[C20H16NOS{OPPh2-Ru（ηBergamini et al. (2004)6-p-花香烃）Cl2}](3)、[C20H16NOS{OPPh2-Ru（ηBergamini et al.(2004)6-苯）Cl2}](4)、[C20H16NOS{OPPh2-Ir(ηGaw et al. (2002)5- c5me5)Cl2}](5)和[C20H16NOS{OPPh2-Rh(cod)Cl}](6)配合物的抗氧化、抗菌和DNA结合活性。为了确定配合物的抗氧化活性，测定了DPPH（2,2-二苯基-1-苦味酰肼）自由基清除能力、金属螯合能力和还原能力。在200.0 mgL−1浓度下，配合物4具有最强的自由基清除能力（74.53±1.76%）和金属螯合活性（63.91±1.54%），而配合物3具有最强的还原能力。对四种病原菌进行抑菌活性测定。只有钌配合物3和4对两种革兰氏阳性菌有较弱的抑菌活性，其他配合物5和6没有抑菌活性。小牛胸腺DNA （CT-DNA）电泳结果显示，所有复合物都具有不同速率的DNA结合活性。
{"title":"Synthesis of new generation amido-Phosphinite derivative complexes by microwave method and investigation of their biological activities","authors":"Saniya Assylbekova , Nermin Meriç , Cezmi Kayan , Ertan Şahin , Alexey Zazybin , Veysi Okumuş , Seval Çelik Zararsiz , Feyyaz Durap , Akın Baysal , Murat Aydemir","doi":"10.1016/j.poly.2025.117818","DOIUrl":"10.1016/j.poly.2025.117818","url":null,"abstract":"<div><div>Several biological activities such as antioxidant, antibacterial, and DNA binding of ruthenium, iridium, and rhodium complexes of a phosphinite were investigated. For this purpose, firstly, a new amide was synthesized from the reaction of 2-(phenylthio)aniline with DL-mandelic acid in a solvent-free environment using microwave irradiation. Subsequently, this amide was converted to its phosphinite counterpart. Then, Ru(II), Ir(III), and Rh(I) complexes (<strong>3–6</strong>) of the phosphinite were synthesized and characterized by several techniques such as microanalysis, IR, and NMR spectroscopy, and in the case of <strong>4</strong> by single crystal X-ray crystallography. Finally, antioxidant, antimicrobial, and DNA binding activities of [C<sub>20</sub>H<sub>16</sub>NOS{OPPh<sub>2</sub>-Ru(ηBergamini et al. (2004)<sup>6</sup>-<em>p</em>-cymene)Cl<sub>2</sub>}] (<strong>3</strong>), [C<sub>20</sub>H<sub>16</sub>NOS{OPPh<sub>2</sub>-Ru(ηBergamini et al. (2004)<sup>6</sup>-benzene)Cl<sub>2</sub>}] (<strong>4</strong>), [C<sub>20</sub>H<sub>16</sub>NOS{OPPh<sub>2</sub>-Ir(ηGaw et al. (2002)<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Cl<sub>2</sub>}] (<strong>5</strong>), and [C<sub>20</sub>H<sub>16</sub>NOS{OPPh<sub>2</sub>-Rh(<em>cod</em>)Cl}] (<strong>6</strong>) complexes were tested. To determine antioxidant activities of the complexes, DPPH (2,2-diphenyl-1-picryl hydrazyl) free radical scavenging, metal chelation, and reducing power activities were measured. At 200.0 mgL<sup>−1</sup> concentration, complex <strong>4</strong> showed the highest radical scavenging (74.53 ± 1.76 %) and metal chelating activity (63.91 ± 1.54 %), while complex <strong>3</strong> exhibited the highest reducing power activity. Antibacterial activity of the compounds was determined with four pathogenic bacteria. Only ruthenium complexes <strong>3</strong> and <strong>4</strong> had weak activity against two Gram-positive bacteria, while the other complexes (<strong>5</strong> and <strong>6</strong>) did not show any antibacterial activity. Electrophoresis results using calf thymus DNA (CT-DNA) displayed that all complexes had DNA binding activity at different rates.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117818"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322561","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 : 2026-01-01Epub Date: 2025-10-24DOI: 10.1016/j.poly.2025.117819
Xingru Liu , Huizhong Wu , Yingdi Zhang, Xicheng Deng, Haoyue Xu, WangYe, Yingxi Wang , Ling Li
A series of bimetallic Co/Ce-MOFs materials (Co/Ce-MOFs-NH2) were synthesized via a solvothermal method, and their catalytic performance in peroxymonosulfate (PMS) activation for the degradation of Rhodamine B (RhB) was systematically investigated. The results demonstrate that the 3:1 Co/Ce-MOFs-NH2 not only retains high catalytic activity but also exhibits significantly enhanced structural stability due to the introduction of Ce3+. Over 99 % of RhB was degraded within 3 min, and the material maintained 92.3 % of its initial activity after five consecutive cycles. Mechanistic studies revealed that ·OH and singlet oxygen (1O2) serves as the dominant reactive oxygen species, while the synergistic redox cycles of Co2+/Co3+ and Ce3+/Ce4+ effectively promote the continuous activation of PMS. This study provides a novel strategy for designing highly efficient and stable bimetallic Metal-Organic Frameworks(MOFs) catalysts.
{"title":"Activating peroxymonosulfate with Co/Ce bimetallic metal-organic frameworks: structural stability and enhanced dye degradation","authors":"Xingru Liu , Huizhong Wu , Yingdi Zhang, Xicheng Deng, Haoyue Xu, WangYe, Yingxi Wang , Ling Li","doi":"10.1016/j.poly.2025.117819","DOIUrl":"10.1016/j.poly.2025.117819","url":null,"abstract":"<div><div>A series of bimetallic Co/Ce-MOFs materials (Co/Ce-MOFs-NH<sub>2</sub>) were synthesized via a solvothermal method, and their catalytic performance in peroxymonosulfate (PMS) activation for the degradation of Rhodamine B (RhB) was systematically investigated. The results demonstrate that the 3:1 Co/Ce-MOFs-NH<sub>2</sub> not only retains high catalytic activity but also exhibits significantly enhanced structural stability due to the introduction of Ce<sup>3+</sup>. Over 99 % of RhB was degraded within 3 min, and the material maintained 92.3 % of its initial activity after five consecutive cycles. Mechanistic studies revealed that <strong>·</strong>OH and singlet oxygen (<sup>1</sup>O<sub>2</sub>) serves as the dominant reactive oxygen species, while the synergistic redox cycles of Co<sup>2+</sup>/Co<sup>3+</sup> and Ce<sup>3+</sup>/Ce<sup>4+</sup> effectively promote the continuous activation of PMS. This study provides a novel strategy for designing highly efficient and stable bimetallic Metal-Organic Frameworks(MOFs) catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117819"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145417768","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 : 2026-01-01Epub Date: 2025-10-27DOI: 10.1016/j.poly.2025.117862
Harshita Srivastava, Ambrish Kumar Srivastava
We present a computational study on oxygen-centered superalkali clusters, OnLi2n+1+ (n = 1–5), constructed by sequential addition of OLi2 units. Optimized geometries and electronic analyses confirm stable configurations with distinct symmetries and pronounced superalkali behavior. The VEA values confirm a strong electron-trapping ability, with OLi3+ exhibiting the highest value (3.459 eV), while larger clusters show structural sensitivity through non-monotonic variations. The Egap decreases systematically from 10.53 eV (OLi3+) to 8.93 eV (O5Li11+), indicating enhanced frontier orbital delocalization and increasing chemical reactivity with cluster size, while maintaining reasonable electronic stability. QTAIM analysis reveals that OLi bonds are mainly ionic, supported by moderate electron density (ρ ≈ 0.04 a.u.) and positive Laplacian, with a slight covalent character in specific cases. These features strengthen the structural robustness and unusual electronic properties of the clusters. Overall, the OnLi2n+1+ series represents a new class of oxygen-centered superalkalis with potential implications for molecular activation, redox chemistry, and hydrogen storage applications.
我们提出了一个氧中心超碱簇OnLi2n+1+ (n = 1 - 5)的计算研究，它是由OLi2单元的顺序加法构造的。优化的几何形状和电子分析证实了具有独特对称性和明显超碱行为的稳定结构。VEA值证实了其较强的电子捕获能力，其中OLi3+表现出最高的值（3.459 eV），而较大的团簇通过非单调变化表现出结构敏感性。Egap从10.53 eV （OLi3+）下降到8.93 eV (O5Li11+)，表明边界轨道离域增强，化学反应性随簇大小而增加，同时保持了合理的电子稳定性。QTAIM分析表明，OLi键主要是离子键，由中等电子密度（ρ≈0.04 a.u.）和正拉普拉斯键支撑，在特定情况下具有轻微的共价特征。这些特点加强了结构的坚固性和不寻常的电子性质的集群。总的来说，OnLi2n+1+系列代表了一类新的以氧为中心的超碱，在分子活化、氧化还原化学和储氢应用方面具有潜在的意义。
{"title":"Computational exploitation of OnLi2n+1+ (n = 1–5): A new oxygen-centred series of superalkali clusters","authors":"Harshita Srivastava, Ambrish Kumar Srivastava","doi":"10.1016/j.poly.2025.117862","DOIUrl":"10.1016/j.poly.2025.117862","url":null,"abstract":"<div><div>We present a computational study on oxygen-centered superalkali clusters, O<sub><em>n</em></sub>Li<sub>2<em>n</em>+1</sub><sup>+</sup> (<em>n</em> = 1–5), constructed by sequential addition of OLi<sub>2</sub> units. Optimized geometries and electronic analyses confirm stable configurations with distinct symmetries and pronounced superalkali behavior. The VEA values confirm a strong electron-trapping ability, with OLi<sub>3</sub><sup>+</sup> exhibiting the highest value (3.459 eV), while larger clusters show structural sensitivity through non-monotonic variations. The <em>E</em><sub>gap</sub> decreases systematically from 10.53 eV (OLi<sub>3</sub><sup>+</sup>) to 8.93 eV (O<sub>5</sub>Li<sub>11</sub><sup>+</sup>), indicating enhanced frontier orbital delocalization and increasing chemical reactivity with cluster size, while maintaining reasonable electronic stability. QTAIM analysis reveals that O<img>Li bonds are mainly ionic, supported by moderate electron density (<em>ρ</em> ≈ 0.04 a.u.) and positive Laplacian, with a slight covalent character in specific cases. These features strengthen the structural robustness and unusual electronic properties of the clusters. Overall, the O<sub><em>n</em></sub>Li<sub>2<em>n</em>+1</sub><sup>+</sup> series represents a new class of oxygen-centered superalkalis with potential implications for molecular activation, redox chemistry, and hydrogen storage applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117862"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145417770","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 : 2026-01-01Epub Date: 2025-10-18DOI: 10.1016/j.poly.2025.117852
Bartosz Cieśla , Łukasz Ponikiewski , Piotr Bruździak , Zbigniew Hnatejko , Renata Łyszczek , Agnieszka Pladzyk
Four new coordination compounds [Zn₂{SSi(OtBu)₃}₄(μ-mepyz)] (1), [Zn{SSi(OtBu)₃}₂(etpyz)] (2), [Cd₂{SSi(OtBu)₃}₄(μ-mepyz)] (3), and {(μ-etpyz)[Cd{SSi(OtBu)₃}₂][Cd{SSi(OtBu)₃}₂(etpyz)]} (4) were synthesized using tri-tert-butoxysilanethiol (TBST) and π-deficient N-donor ligands methylpyrazine (mepyz) and ethylpyrazine (etpyz). Structural characterization revealed diverse coordination modes, with TBST acting as either terminal or bridging ligands. Spectroscopic and thermal analyses, supported by DFT/TD-DFT calculations demonstrated intramolecular charge transfer and luminescence properties originating from pyrazine-metal interactions. While complexes 1–4 exhibited no catalytic activity in reactions of the oligomerization of allyl alcohol and also no antimicrobiological properties, these findings establish structure-property relationships for the rational design of functional silanethiolate-based materials.
{"title":"The impact of pyrazine derivatives on the structure and luminescence of Zn(II)/Cd(II) tri-tert-butoxysilanethiolate complexes. A combined spectroscopic and computational study","authors":"Bartosz Cieśla , Łukasz Ponikiewski , Piotr Bruździak , Zbigniew Hnatejko , Renata Łyszczek , Agnieszka Pladzyk","doi":"10.1016/j.poly.2025.117852","DOIUrl":"10.1016/j.poly.2025.117852","url":null,"abstract":"<div><div>Four new coordination compounds [Zn₂{SSi(O<em>t</em>Bu)₃}₄(<em>μ</em>-mepyz)] (<strong>1</strong>), [Zn{SSi(O<em>t</em>Bu)₃}₂(etpyz)] (<strong>2</strong>), [Cd₂{SSi(O<em>t</em>Bu)₃}₄(<em>μ</em>-mepyz)] (<strong>3</strong>), and {(<em>μ</em>-etpyz)[Cd{SSi(O<em>t</em>Bu)₃}₂][Cd{SSi(O<em>t</em>Bu)₃}₂(etpyz)]} (<strong>4</strong>) were synthesized using tri-<em>tert</em>-butoxysilanethiol (TBST) and π-deficient N-donor ligands methylpyrazine (mepyz) and ethylpyrazine (etpyz). Structural characterization revealed diverse coordination modes, with TBST acting as either terminal or bridging ligands. Spectroscopic and thermal analyses, supported by DFT/TD-DFT calculations demonstrated intramolecular charge transfer and luminescence properties originating from pyrazine-metal interactions. While complexes <strong>1</strong>–<strong>4</strong> exhibited no catalytic activity in reactions of the oligomerization of allyl alcohol and also no antimicrobiological properties, these findings establish structure-property relationships for the rational design of functional silanethiolate-based materials<em>.</em></div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117852"},"PeriodicalIF":2.6,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145364374","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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