Pub Date : 2025-11-22DOI: 10.1016/j.poly.2025.117903
Daniele M. Martins, Eliada A. Silva, Benedito S. Lima-Neto
The fac-[RuCl₂(dmap)(S-dmso)₃] complex, where dmap is 4-dimethylaminopyridine, was synthesized in a single step at room temperature and can be stored under ambient conditions without the need for strict exclusion of molecular oxygen or moisture. Kinetic studies of the complex's activity in the ring-opening metathesis polymerization (ROMP) of norbornene, in the presence of ethyl diazoacetate (EDA), were conducted using 1H NMR spectroscopy. The active Ru-carbene species was formed in situ, as confirmed by 1H NMR and mass spectrometry analyses, and initiated the ROMP process immediately. At low monomer concentrations, or in the absence of monomer, isomeric dimers of EDA, diethyl maleate and diethyl fumarate, were produced. A mechanism is proposed for both the homocoupling of EDA and the ROMP reaction, each proceeding via the same Ru-carbene intermediate in a competitive pathway. This study highlights the potential for the straightforward synthesis of low-cost amine-Ru-dmso complexes that function as pre-catalysts in various reactions, with particular emphasis on the use of the dmso molecule as a versatile ancillary ligand.
face -[RuCl₂（dmap）（S-dmso）₃]配合物，其中dmap是4-二甲氨基吡啶，在室温下一步合成，可以在环境条件下储存，而不需要严格排除分子氧或水分。用1H NMR研究了该配合物在重氮乙酸乙酯（EDA）存在下降冰片烯开环复分解聚合（ROMP）反应中的活性。经1H NMR和质谱分析证实，活性的Ru-carbene物种在原位形成，并立即启动了ROMP过程。在低单体浓度下，或在没有单体的情况下，EDA的异构体，马来酸二乙酯和富马酸二乙酯，被生产出来。本文提出了一种EDA同偶联和ROMP反应的机制，它们都是通过相同的Ru-carbene中间体在竞争途径中进行的。本研究强调了直接合成低成本胺- ru -dmso配合物的潜力，该配合物在各种反应中作为预催化剂，特别强调了dmso分子作为多功能辅助配体的使用。
{"title":"Kinetic study of the ruthenium-dmso complex with 4-dimethylaminopyridine in the ROMP reaction of norbornene by NMR spectroscopy","authors":"Daniele M. Martins, Eliada A. Silva, Benedito S. Lima-Neto","doi":"10.1016/j.poly.2025.117903","DOIUrl":"10.1016/j.poly.2025.117903","url":null,"abstract":"<div><div>The <em>fac</em>-[RuCl₂(dmap)(S-dmso)₃] complex, where dmap is 4-dimethylaminopyridine, was synthesized in a single step at room temperature and can be stored under ambient conditions without the need for strict exclusion of molecular oxygen or moisture. Kinetic studies of the complex's activity in the ring-opening metathesis polymerization (ROMP) of norbornene, in the presence of ethyl diazoacetate (EDA), were conducted using <sup>1</sup>H NMR spectroscopy. The active Ru-carbene species was formed in situ, as confirmed by <sup>1</sup>H NMR and mass spectrometry analyses, and initiated the ROMP process immediately. At low monomer concentrations, or in the absence of monomer, isomeric dimers of EDA, diethyl maleate and diethyl fumarate, were produced. A mechanism is proposed for both the homocoupling of EDA and the ROMP reaction, each proceeding via the same Ru-carbene intermediate in a competitive pathway. This study highlights the potential for the straightforward synthesis of low-cost amine-Ru-dmso complexes that function as pre-catalysts in various reactions, with particular emphasis on the use of the dmso molecule as a versatile ancillary ligand.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117903"},"PeriodicalIF":2.6,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748527","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 : 2025-11-22DOI: 10.1016/j.poly.2025.117876
Maroj Bharati , Vikram Singh , Ram Kripal
The superposition model is used to calculate the zero field splitting parameters for Zn (NH4)2(SO4)2.6H2O (ZAS) single crystals doped with Mn2+. The evaluated parameters agree well with those of the EPR experiment. The experimental conclusion that in ZAS, the Mn2+ ion takes the place of the Zn2+ site is confirmed by theoretical studies. Crystal's optical spectra are estimated by the diagonalization of full Hamiltonian utilizing crystal field parameters obtained from the superposition model and crystal field analysis computer program. The experimental bands' positions and calculations agree fairly well. Consequently, the experimental results are confirmed by the theoretical analysis.
{"title":"Optical absorption, local structure and zero field splitting of Zn(NH4)2(SO4)2·6H2O:Mn single crystals","authors":"Maroj Bharati , Vikram Singh , Ram Kripal","doi":"10.1016/j.poly.2025.117876","DOIUrl":"10.1016/j.poly.2025.117876","url":null,"abstract":"<div><div>The superposition model is used to calculate the zero field splitting parameters for Zn (NH<sub>4</sub>)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>.6H<sub>2</sub>O (ZAS) single crystals doped with Mn<sup>2+</sup>. The evaluated parameters agree well with those of the EPR experiment. The experimental conclusion that in ZAS, the Mn<sup>2+</sup> ion takes the place of the Zn<sup>2+</sup> site is confirmed by theoretical studies. Crystal's optical spectra are estimated by the diagonalization of full Hamiltonian utilizing crystal field parameters obtained from the superposition model and crystal field analysis computer program. The experimental bands' positions and calculations agree fairly well. Consequently, the experimental results are confirmed by the theoretical analysis.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117876"},"PeriodicalIF":2.6,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621346","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 : 2025-11-21DOI: 10.1016/j.poly.2025.117906
M. Mohammadi, S.A. Kahani
The bimetallic CoNi (S1) and FeNi (S2) nano-alloys were synthesized by chemical co-reduction of theirs MCl2 (M = FeII, CoII and NiII) salts by aluminum nanoparticles in an acidic solid-state reaction at room temperature. The products were characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy-dispersive X-ray (EDX), and vibrating sample magnetometer (VSM). The X-ray diffraction patterns of products S1 and S2 revealed the presence of intermetallic, metallic, and unreacted aluminum phases. The products weight fractions were calculated using Rietveld refinement. Quantitative XRD analysis of S1 shows a weight fraction of CoNi 58.58 wt%, Co 6.04 wt%, Ni 30.14 wt% and unreacted aluminum 5.23 wt%. Whereas, calculation in S2 shows weight fraction FeNi, Fe, Ni and unreacted aluminum 22.87, 44.20, 18.16 and 14.77 wt% respectively. The weight fraction of the intermetallic CoNi phase is more than the intermetallic FeNi phase which is associated with Hum-Ruhter rules for the alloy formation, such as electronegativity, as explained in the Van Arkel-Ketelaar triangle. FESEM image of S1 and S2 show particles size distribution in the region 40–140 nm and 30–130 nm respectively. The hysteresis loop of S1 and S2 show magnetic saturation 88.374 emu/g and 61.298 emu/g respectively.
{"title":"Mechanochemical synthesis of bimetallic FeNi and CoNi nano-alloys at room temperature","authors":"M. Mohammadi, S.A. Kahani","doi":"10.1016/j.poly.2025.117906","DOIUrl":"10.1016/j.poly.2025.117906","url":null,"abstract":"<div><div>The bimetallic CoNi (S<sub>1</sub>) and FeNi (S<sub>2</sub>) nano-alloys were synthesized by chemical co-reduction of theirs MCl<sub>2</sub> (M = Fe<sup>II</sup>, Co<sup>II</sup> and Ni<sup>II</sup>) salts by aluminum nanoparticles in an acidic solid-state reaction at room temperature. The products were characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy-dispersive X-ray (EDX), and vibrating sample magnetometer (VSM). The X-ray diffraction patterns of products S<sub>1</sub> and S<sub>2</sub> revealed the presence of intermetallic, metallic, and unreacted aluminum phases. The products weight fractions were calculated using Rietveld refinement. Quantitative XRD analysis of S<sub>1</sub> shows a weight fraction of CoNi 58.58 wt%, Co 6.04 wt%, Ni 30.14 wt% and unreacted aluminum 5.23 wt%. Whereas, calculation in S<sub>2</sub> shows weight fraction FeNi, Fe, Ni and unreacted aluminum 22.87, 44.20, 18.16 and 14.77 wt% respectively. The weight fraction of the intermetallic CoNi phase is more than the intermetallic FeNi phase which is associated with Hum-Ruhter rules for the alloy formation, such as electronegativity, as explained in the Van Arkel-Ketelaar triangle. FESEM image of S<sub>1</sub> and S<sub>2</sub> show particles size distribution in the region 40–140 nm and 30–130 nm respectively. The hysteresis loop of S<sub>1</sub> and S<sub>2</sub> show magnetic saturation 88.374 emu/g and 61.298 emu/g respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117906"},"PeriodicalIF":2.6,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621421","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 : 2025-11-19DOI: 10.1016/j.poly.2025.117901
Shuchang Luo , Jun Zhao , Lingdong Liu , Hao Yang , Xiaoyuan Sun
This study investigates the influence of axial ligand substituents (1-AdO (1), –OtBu (2), –OCH3 (3), –OC2H5 (4), –OC3H7 (5), –OiPr (6), –OC6H5 (7), –O–C(CF3)3 (8), –S–C(CH3)3 (9), –Se–C(CH3)3 (10), and –N(CH3)2 (11)), Dy–Oaxi bond lengths, and Oaxi–Dy–Oaxi bond angles on the magnetic properties of alkoxy-coordinated [Dy(18-C-6)L2]+ complexes through ab initio calculations on air-stable crown dysprosium(III)-based single-molecule magnets (Dy-SMMs). The magnetic performance of this series of SMMs can be preliminarily evaluated based on the quantum tunnelling of magnetization time (τQTM) and effective energy barrier (Ueff). Among these complexes, the OtBu-substituted derivative, featuring a linear Oaxi–Dy–Oaxi bond angle of 180° and an optimal Dy–Oaxi bond length of 1.95 Å, exhibits the highest blocking temperature, longest τQTM, and highest Ueff. These findings provide crucial theoretical insights for understanding the magnetic nature of Dy-SMMs and guiding the design of high-performance SMMs.
{"title":"The effect of axial ligands on the magnetic properties of oxygen-coordinated Dy-SMMs: Theoretical insights","authors":"Shuchang Luo , Jun Zhao , Lingdong Liu , Hao Yang , Xiaoyuan Sun","doi":"10.1016/j.poly.2025.117901","DOIUrl":"10.1016/j.poly.2025.117901","url":null,"abstract":"<div><div>This study investigates the influence of axial ligand substituents (1-AdO (<strong>1</strong>), –O<sup>t</sup>Bu (<strong>2</strong>), –OCH<sub>3</sub> (<strong>3</strong>), –OC<sub>2</sub>H<sub>5</sub> (<strong>4</strong>), –OC<sub>3</sub>H<sub>7</sub> (<strong>5</strong>), –O<sup>i</sup>Pr (<strong>6</strong>), –OC<sub>6</sub>H<sub>5</sub> (<strong>7</strong>), –O–C(CF<sub>3</sub>)<sub>3</sub> (<strong>8</strong>), –S–C(CH<sub>3</sub>)<sub>3</sub> (<strong>9</strong>), –Se–C(CH<sub>3</sub>)<sub>3</sub> (<strong>10</strong>), and –N(CH<sub>3</sub>)<sub>2</sub> (<strong>11</strong>)), Dy–O<sub>axi</sub> bond lengths, and O<sub>axi</sub>–Dy–O<sub>axi</sub> bond angles on the magnetic properties of alkoxy-coordinated [Dy(18-C-6)L<sub>2</sub>]<sup>+</sup> complexes through ab initio calculations on air-stable crown dysprosium(III)-based single-molecule magnets (Dy-SMMs). The magnetic performance of this series of SMMs can be preliminarily evaluated based on the quantum tunnelling of magnetization time (<em>τ</em><sub>QTM</sub>) and effective energy barrier (<em>U</em><sub>eff</sub>). Among these complexes, the O<sup>t</sup>Bu-substituted derivative, featuring a linear O<sub>axi</sub>–Dy–O<sub>axi</sub> bond angle of 180° and an optimal Dy–O<sub>axi</sub> bond length of 1.95 Å, exhibits the highest blocking temperature, longest <em>τ</em><sub>QTM</sub>, and highest <em>U</em><sub>eff</sub>. These findings provide crucial theoretical insights for understanding the magnetic nature of Dy-SMMs and guiding the design of high-performance SMMs.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117901"},"PeriodicalIF":2.6,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577692","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 : 2025-11-19DOI: 10.1016/j.poly.2025.117892
Feng-Li Chen , Ao-Na Sun , Jiong Yang , Bo Chen , Jiang-Ping Qin , Dong Shao
A metal hydrogen-bonded organic frameworks (MHOFs) constructed from a 1D Fe(II) coordination polymer, {[Fe(bpy)·(H2O)4]·2ClO4·2bpy·2H2O}n (Fe, bpy = 4,4’-Bipyridine) was structurally, magnetically, and electrically characterized. Structural analysis indicates the presence of a high content of coordinated water and lattice water molecules, which form multiple hydrogen-bonded interactions with perchlorate anions and free bpy ligands. Combining the intermolecular π–π stacking interactions, a 3D supramolecular framework was formed. Magnetic measurements reveal high spin of the Fe2+ ions in FeHOF, in conjunction with variable-temperature single-crystal X-ray diffraction analysis. In addition, weak antiferromagnetic interaction between the Fe2+ ions transferred by bpy (J = −1.3 cm−1) was evidenced. Electrochemical impedance spectroscopy (EIS) indicates the FeHOF temperature and -humidity dependent proton conduction behavior through a vehicle mechanism (Ea = 0.45 eV). The highest observed conductivity was 6.2 × 10−5 S·cm−1 at 60 °C under 95% RH, indicating a supramolecular proton conductor of the FeHOF. The foregoing results not only provide a new proton-conducting MHOF material but also a promising way to construct proton-conducting MHOFs via a coordination chain approach
{"title":"Synthesis, structure, magnetic property, and proton conduction of a hydrogen-bonded framework assembled from Fe(II) coordination chains","authors":"Feng-Li Chen , Ao-Na Sun , Jiong Yang , Bo Chen , Jiang-Ping Qin , Dong Shao","doi":"10.1016/j.poly.2025.117892","DOIUrl":"10.1016/j.poly.2025.117892","url":null,"abstract":"<div><div>A metal hydrogen-bonded organic frameworks (MHOFs) constructed from a 1D Fe(II) coordination polymer, {[Fe(bpy)·(H<sub>2</sub>O)<sub>4</sub>]·2ClO<sub>4</sub>·2bpy·2H<sub>2</sub>O}<sub>n</sub> (<strong>Fe</strong>, bpy = 4,4’-Bipyridine) was structurally, magnetically, and electrically characterized. Structural analysis indicates the presence of a high content of coordinated water and lattice water molecules, which form multiple hydrogen-bonded interactions with perchlorate anions and free bpy ligands. Combining the intermolecular π–π stacking interactions, a 3D supramolecular framework was formed. Magnetic measurements reveal high spin of the Fe<sup>2+</sup> ions in FeHOF, in conjunction with variable-temperature single-crystal X-ray diffraction analysis. In addition, weak antiferromagnetic interaction between the Fe<sup>2+</sup> ions transferred by bpy (<em>J</em> = −1.3 cm<sup>−1</sup>) was evidenced. Electrochemical impedance spectroscopy (EIS) indicates the FeHOF temperature and -humidity dependent proton conduction behavior through a vehicle mechanism (<em>E</em><sub>a</sub> = 0.45 eV). The highest observed conductivity was 6.2 × 10<sup>−5</sup> S·cm<sup>−1</sup> at 60 °C under 95% RH, indicating a supramolecular proton conductor of the FeHOF. The foregoing results not only provide a new proton-conducting MHOF material but also a promising way to construct proton-conducting MHOFs via a coordination chain approach</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117892"},"PeriodicalIF":2.6,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577688","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 : 2025-11-19DOI: 10.1016/j.poly.2025.117904
Syahrina Nur 'Ain Abdul Halim , Khomaizon Abdul Kadir Pahirul Zaman , Siti Nadiah Abdul Halim , Pei Meng Woi , Rozie Sarip
Two new gold(I) thiosemicarbazone phosphine complexes have been synthesised and characterised using various spectroscopic techniques and single-crystal X-ray diffraction. In these complexes, the gold atom is coordinated with the sulphur of thiosemicarbazone and phosphorus of triphenylphosphine, resulting in a linear structure. These complexes were also employed as precursors for the synthesis of Au monometallic clusters, resulting in very refined nanosized particles that were analysed using electrospray ionisation mass spectroscopy (ESI-MS), UV–Visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission microscopy (HR-TEM). Furthermore, cyclic voltammetry (CV) analysis was conducted to evaluate the electrochemical properties of the complexes and clusters. The antibacterial properties of these nanoclusters, complexes, as well as their free thiosemicarbazone ligands, were assessed against gram-positive Staphylococcus aureus and gram-negative Escherichia coli. While the free ligands exhibited a considerable antibacterial activity, their corresponding Au(I) complexes showed diminished efficacy against both bacterial strains. In contrast, the nanoclusters demonstrated notable activity against S. aureus but proved ineffective against E. coli.
{"title":"From monomers to nanoclusters: Synthesis, characterisation and antibacterial evaluation of gold (I) complexes and their nanoclusters containing thiosemicarbazone and phosphine ligands","authors":"Syahrina Nur 'Ain Abdul Halim , Khomaizon Abdul Kadir Pahirul Zaman , Siti Nadiah Abdul Halim , Pei Meng Woi , Rozie Sarip","doi":"10.1016/j.poly.2025.117904","DOIUrl":"10.1016/j.poly.2025.117904","url":null,"abstract":"<div><div>Two new gold(I) thiosemicarbazone phosphine complexes have been synthesised and characterised using various spectroscopic techniques and single-crystal X-ray diffraction. In these complexes, the gold atom is coordinated with the sulphur of thiosemicarbazone and phosphorus of triphenylphosphine, resulting in a linear structure. These complexes were also employed as precursors for the synthesis of Au monometallic clusters, resulting in very refined nanosized particles that were analysed using electrospray ionisation mass spectroscopy (ESI-MS), UV–Visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission microscopy (HR-TEM). Furthermore, cyclic voltammetry (CV) analysis was conducted to evaluate the electrochemical properties of the complexes and clusters. The antibacterial properties of these nanoclusters, complexes, as well as their free thiosemicarbazone ligands, were assessed against gram-positive <em>Staphylococcus aureus</em> and gram-negative <em>Escherichia coli</em>. While the free ligands exhibited a considerable antibacterial activity, their corresponding Au(I) complexes showed diminished efficacy against both bacterial strains. In contrast, the nanoclusters demonstrated notable activity against <em>S. aureus</em> but proved ineffective against <em>E. coli</em>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117904"},"PeriodicalIF":2.6,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621350","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 : 2025-11-19DOI: 10.1016/j.poly.2025.117900
Nitin H. Kolhe , Yasinalli Tamboli , Huda A. Bawazir , Vijay Singh Parihar
Mixed-ligand transition metal complexes have emerged as a significant area of research due to their tunable structural, electronic, and biological properties. This comprehensive review provides a detailed analysis of recent advances in the synthesis, characterization, and diverse applications of complexes formed by combining 3-formylchromone derivatives with auxiliary N, O-donor ligand 8-hydroxyquinoline. We systematically explore the coordination chemistry of chromone, a versatile pharmacophore, highlighting its role as a primary ligand. A critical examination of their biological properties, including antimicrobial, anticancer, and antioxidant activities, is presented. Furthermore, the review elucidates the key structure-activity relationships (SARs) that govern their efficacy. By compiling the current state of knowledge, this work aims to identify existing research gaps and propose future directions for the rational design of next-generation mixed-ligand complexes with tailored properties for advanced applications in medicine.
{"title":"Advances in mixed ligand transition metal complexes: Chromone derivatives and N, O donor ligands – a comprehensive review","authors":"Nitin H. Kolhe , Yasinalli Tamboli , Huda A. Bawazir , Vijay Singh Parihar","doi":"10.1016/j.poly.2025.117900","DOIUrl":"10.1016/j.poly.2025.117900","url":null,"abstract":"<div><div>Mixed-ligand transition metal complexes have emerged as a significant area of research due to their tunable structural, electronic, and biological properties. This comprehensive review provides a detailed analysis of recent advances in the synthesis, characterization, and diverse applications of complexes formed by combining 3-formylchromone derivatives with auxiliary N, O-donor ligand 8-hydroxyquinoline. We systematically explore the coordination chemistry of chromone, a versatile pharmacophore, highlighting its role as a primary ligand. A critical examination of their biological properties, including antimicrobial, anticancer, and antioxidant activities, is presented. Furthermore, the review elucidates the key structure-activity relationships (SARs) that govern their efficacy. By compiling the current state of knowledge, this work aims to identify existing research gaps and propose future directions for the rational design of next-generation mixed-ligand complexes with tailored properties for advanced applications in medicine.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117900"},"PeriodicalIF":2.6,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621352","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 : 2025-11-19DOI: 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":"2025-11-19","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}
Pub Date : 2025-11-19DOI: 10.1016/j.poly.2025.117899
A. Tesmar , A. Sikorski , P. Niedziałkowski , B. Matusiewicz , I. Inkielewicz-Stępniak , D. Wyrzykowski
The nature of the counterions is a key factor in designing nitrilotriacetate (nta) oxidovanadium(IV) salts. Selecting the appropriate counterion affects the formation of complexes with either mono- or hetero-ligands in the coordination sphere, as well as mono- or heteronuclear entities. N-heterocyclic compounds can serve dual roles: they can act as counterions and simultaneously chelate the vanadium(IV) cation, or they can function solely as counterions without directly coordinating with the metal centre. Consequently, it enables the design of new coordination compounds with desirable physicochemical and biological properties. In this article, we present the crystal structure of a novel heteroligand nitrilotriacetate (nta) oxidovanadium(IV) complex salt of a general formula, [(2-NH2–3-OH)pyH)][VO(nta)(2-NH2–3-O-pyH)]∙H2O, where 2-amino-3-hydroxypyridine acts as both a zwitterionic ligand (2-NH2–3-O-pyH)± and a counterion [(2-NH2–3-OH)pyH]+. The physicochemical properties of the newly synthesized complex salt were thoroughly investigated and analyzed, including its ABTS•+ radical scavenging activity and reactivity towards hydrogen peroxide (H2O2). These studies aimed to explore potential structural features of the oxidovanadium(IV) species that may influence their antioxidant activity. Finally, the potential of 2-amino-3-hydroxypyridine and [(2-NH2–3-OH)pyH)][VO(nta)(2-NH2–3-O-pyH)]∙H2O as cytoprotective agents against oxidative damage induced by H2O2 was assessed using the HT22 hippocampal neuronal cell line.
{"title":"A novel heteroligand nitrilotriacetate oxidovanadium(IV) complex salt with 2-amino-3-hydroxypyridine as a zwitterionic ligand and counterion: Structural characterisation, antioxidant activity and cytoprotective potential","authors":"A. Tesmar , A. Sikorski , P. Niedziałkowski , B. Matusiewicz , I. Inkielewicz-Stępniak , D. Wyrzykowski","doi":"10.1016/j.poly.2025.117899","DOIUrl":"10.1016/j.poly.2025.117899","url":null,"abstract":"<div><div>The nature of the counterions is a key factor in designing nitrilotriacetate (nta) oxidovanadium(IV) salts. Selecting the appropriate counterion affects the formation of complexes with either mono- or hetero-ligands in the coordination sphere, as well as mono- or heteronuclear entities. N-heterocyclic compounds can serve dual roles: they can act as counterions and simultaneously chelate the vanadium(IV) cation, or they can function solely as counterions without directly coordinating with the metal centre. Consequently, it enables the design of new coordination compounds with desirable physicochemical and biological properties. In this article, we present the crystal structure of a novel heteroligand nitrilotriacetate (nta) oxidovanadium(IV) complex salt of a general formula, [(2-NH<sub>2</sub>–3-OH)pyH)][VO(nta)(2-NH<sub>2</sub>–3-O-pyH)]∙H<sub>2</sub>O, where 2-amino-3-hydroxypyridine acts as both a zwitterionic ligand (2-NH<sub>2</sub>–3-O-pyH)<sup>±</sup> and a counterion [(2-NH<sub>2</sub>–3-OH)pyH]<sup>+</sup>. The physicochemical properties of the newly synthesized complex salt were thoroughly investigated and analyzed, including its ABTS<sup>•+</sup> radical scavenging activity and reactivity towards hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). These studies aimed to explore potential structural features of the oxidovanadium(IV) species that may influence their antioxidant activity. Finally, the potential of 2-amino-3-hydroxypyridine and [(2-NH<sub>2</sub>–3-OH)pyH)][VO(nta)(2-NH<sub>2</sub>–3-O-pyH)]∙H<sub>2</sub>O as cytoprotective agents against oxidative damage induced by H<sub>2</sub>O<sub>2</sub> was assessed using the HT22 hippocampal neuronal cell line.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117899"},"PeriodicalIF":2.6,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621348","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 : 2025-11-17DOI: 10.1016/j.poly.2025.117898
Zhen-Yu Yang, Jia-Lu Guan, Jin-Sheng Zhang, Ju-Wen Zhang, Yan Zhao, Bin-Qiu Liu
In this paper, a series of Ni(II)-Ln(III) heterometallic complexes [Ln2Ni2(2,3-DCB)10(4,4′-dm-2,2′-bpy)2] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Yb (7), 2,3-HDCB = 2,3-dichlorobenzoic acid, 4,4′-dm-2,2′-bpy = 4,4′-dimethyl-2,2′-bipyridine] were solvothermally synthesized and structurally characterized. Complexes 1–7 have the same molecular formula but different molecular structures. Complexes 1–6 are isostructural. Complexes 1–7 all show zero-dimensional (0D) linear tetranuclear cluster structures, and the adjacent molecules can be linked through the π–π interactions between 4,4′-dm-2,2′-bipy into a one-dimensional (1D) supramolecular chain. Complex 6 exhibits the ferromagnetic couplings between the metal ions and obvious field-dependent single-molecule magnet (SMM) behavior with an effective energy barrier (Ueff) of approximately 13 K. Introduction of two methyl groups in 2,2′-bipy has an important effect on the structures and magnetic properties of Ni(II)-Ln(III) heterometallic complexes.
{"title":"Syntheses, structures and magnetic properties of a series of nickel-lanthanide heterometallic complexes with mixed ligands of 2,3-dichlorobenzoate and 4,4′-dimethyl-2,2′-bipyridine","authors":"Zhen-Yu Yang, Jia-Lu Guan, Jin-Sheng Zhang, Ju-Wen Zhang, Yan Zhao, Bin-Qiu Liu","doi":"10.1016/j.poly.2025.117898","DOIUrl":"10.1016/j.poly.2025.117898","url":null,"abstract":"<div><div>In this paper, a series of Ni(II)-Ln(III) heterometallic complexes [Ln<sub>2</sub>Ni<sub>2</sub>(2,3-DCB)<sub>10</sub>(4,4′-dm-2,2′-bpy)<sub>2</sub>] [Ln = Nd (<strong>1</strong>), Sm (<strong>2</strong>), Eu (<strong>3</strong>), Gd (<strong>4</strong>), Tb (<strong>5</strong>), Dy (<strong>6</strong>), Yb (<strong>7</strong>), 2,3-HDCB = 2,3-dichlorobenzoic acid, 4,4′-dm-2,2′-bpy = 4,4′-dimethyl-2,2′-bipyridine] were solvothermally synthesized and structurally characterized. Complexes <strong>1</strong>–<strong>7</strong> have the same molecular formula but different molecular structures. Complexes <strong>1</strong>–<strong>6</strong> are isostructural. Complexes <strong>1</strong>–<strong>7</strong> all show zero-dimensional (0D) linear tetranuclear cluster structures, and the adjacent molecules can be linked through the π–π interactions between 4,4′-dm-2,2′-bipy into a one-dimensional (1D) supramolecular chain. Complex <strong>6</strong> exhibits the ferromagnetic couplings between the metal ions and obvious field-dependent single-molecule magnet (SMM) behavior with an effective energy barrier (<em>U</em><sub>eff</sub>) of approximately 13 K. Introduction of two methyl groups in 2,2′-bipy has an important effect on the structures and magnetic properties of Ni(II)-Ln(III) heterometallic complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117898"},"PeriodicalIF":2.6,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577697","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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