Polyhedron最新文献_第6页

Structural characterization, theoretical, and antibacterial activity study of halogen-η3-allylpalladium(II) complexes incorporating 2-, 3- and 4-pyridyl-methylen-4-methylumbelliferone esters

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-22 DOI: 10.1016/j.poly.2025.117414

Willyfredo Fragoso–Soto , Diego Martínez-Otero , Irais Sánchez-Ortega , Julián Cruz–Borbolla , José Manuel Vásquez-Pérez , Simplicio González–Montiel

A series of 2-, 3- and 4-pyridyl-methylen-4-methylumbelliferone esters ligands (1 – 3) and their chloro- and bromo-η³-allylpalladium(II) complexes (Pd1 – Pd6) were designed, synthetized, and characterized. Solution-phase studies by ¹H and ¹³C NMR spectroscopy of Pd1 – Pd6 revealed the presence of the allyl fragment which suggested the coordination of the ligands (1 – 3) towards Pd(II). GIAO/DFT studies were performed to predict the molecular structures of Pd1 – Pd6 by comparing the experimental and theoretical ¹H and ¹³C NMR chemical shifts. The molecular structure of 1, 1a, 2, 3, Pd1 and Pd4 was determined by X-ray crystallographic analysis. The molecular structure of Pd1 and Pd4 reveals that 2-pyridyl-methylen-4-methylumbelliferone ester ligand (1) is coordinated to the palladium (II) center via a monodentate fashion through the nitrogen atom of the pyridinyl fragment and allyl group is binding via a η³ fashion in an overall five-fold coordination geometry completed with a halogen atom (chloro in Pd1 and bromo in Pd4, respectively). The crystal packing is stabilized by a variety of weak intermolecular conventional and non-conventional interactions involving CH•••O/N/Hal hydrogen bonds, π•••π, lone pair•••π and CH•••π interactions, which have been analyzed by Hirshfeld surface analysis. All halogen-η³-allylpalladium(II) complexes displayed potential activities against both Gram-positive (Listeria monocytogenes and Staphylococcus aureus) and Gram-negative (Escherichia coli and Salmonella spp.)

{"title":"Structural characterization, theoretical, and antibacterial activity study of halogen-η3-allylpalladium(II) complexes incorporating 2-, 3- and 4-pyridyl-methylen-4-methylumbelliferone esters","authors":"Willyfredo Fragoso–Soto , Diego Martínez-Otero , Irais Sánchez-Ortega , Julián Cruz–Borbolla , José Manuel Vásquez-Pérez , Simplicio González–Montiel","doi":"10.1016/j.poly.2025.117414","DOIUrl":"10.1016/j.poly.2025.117414","url":null,"abstract":"<div><div>A series of 2-, 3- and 4-pyridyl-methylen-4-methylumbelliferone esters ligands (1 – 3) and their chloro- and bromo-η3-allylpalladium(II) complexes (Pd1 – Pd6) were designed, synthetized, and characterized. Solution-phase studies by 1H and 13C NMR spectroscopy of Pd1 – Pd6 revealed the presence of the allyl fragment which suggested the coordination of the ligands (1 – 3) towards Pd(II). GIAO/DFT studies were performed to predict the molecular structures of Pd1 – Pd6 by comparing the experimental and theoretical 1H and 13C NMR chemical shifts. The molecular structure of 1, 1a, 2, 3, Pd1 and Pd4 was determined by X-ray crystallographic analysis. The molecular structure of Pd1 and Pd4 reveals that 2-pyridyl-methylen-4-methylumbelliferone ester ligand (1) is coordinated to the palladium (II) center via a monodentate fashion through the nitrogen atom of the pyridinyl fragment and allyl group is binding via a η3 fashion in an overall five-fold coordination geometry completed with a halogen atom (chloro in Pd1 and bromo in Pd4, respectively). The crystal packing is stabilized by a variety of weak intermolecular conventional and non-conventional interactions involving C<img>H•••O/N/Hal hydrogen bonds, π•••π, lone pair•••π and C<img>H•••π interactions, which have been analyzed by Hirshfeld surface analysis. All halogen-η3-allylpalladium(II) complexes displayed potential activities against both Gram-positive (Listeria monocytogenes and Staphylococcus aureus) and Gram-negative (Escherichia coli and Salmonella spp.)</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117414"},"PeriodicalIF":2.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148721","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}

引用次数: 0

Bismuth and transition metal complexes as potent anti-Helicobacter pylori agents: A review

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-22 DOI: 10.1016/j.poly.2025.117413

Xiaofeng Zhou, Jian-wei Yun

Helicobacter pylori (Hp) belongs to the genus spirillobacter and generally colonizes the human stomach, frequently causing the various gastric diseases. The conventional antibiotics are often applied for the treatment of Hp infection, but their overuses prompting Hp to form a biofilm will reduce its susceptibility to antibiotics, thus resulting in antibiotic resistance to severely affect the therapy of Hp infection. Interestingly, the eradication rate of Hp increases when antibiotics are combined with bismuth complex-based agents that include colloidal bismuth subcitrate (CBS), bismuth subsalicylate (BSS) and ranitidine bismuth citrate (RBS), due to the synergistic activity of antibiotics and bismuth complexes, while no reports of resistance to bismuth complexes until now, so it is reasonable to select bismuth complex as an indispensable part of first-line therapy. As a result, the trivalent bismuth has been applied for the preparation of various bismuth complexes with efficient anti-Hp activities, appealing as the anti-Hp agents with low toxicity. Subsequently, some transition metal complexes with the better anti-Hp activities are also designed and synthesized. We believe that the development of new bismuth and transition metal complexes as anti-Hp agents may be a promising approach to increase the eradication rate of Hp infection. This review summarizes the most striking advances in the syntheses, crystal structures, and anti-Hp activities of bismuth and transition metal complexes, which attempt to not only reveal a correlation between their structural features and anti-Hp activities, but also offer the helpful guidance for the researchers in the future development of new bismuth and other important bio-metal complexes as the efficient anti-Hp agents.

{"title":"Bismuth and transition metal complexes as potent anti-Helicobacter pylori agents: A review","authors":"Xiaofeng Zhou, Jian-wei Yun","doi":"10.1016/j.poly.2025.117413","DOIUrl":"10.1016/j.poly.2025.117413","url":null,"abstract":"<div><div>Helicobacter pylori (Hp) belongs to the genus spirillobacter and generally colonizes the human stomach, frequently causing the various gastric diseases. The conventional antibiotics are often applied for the treatment of Hp infection, but their overuses prompting Hp to form a biofilm will reduce its susceptibility to antibiotics, thus resulting in antibiotic resistance to severely affect the therapy of Hp infection. Interestingly, the eradication rate of Hp increases when antibiotics are combined with bismuth complex-based agents that include colloidal bismuth subcitrate (CBS), bismuth subsalicylate (BSS) and ranitidine bismuth citrate (RBS), due to the synergistic activity of antibiotics and bismuth complexes, while no reports of resistance to bismuth complexes until now, so it is reasonable to select bismuth complex as an indispensable part of first-line therapy. As a result, the trivalent bismuth has been applied for the preparation of various bismuth complexes with efficient anti-Hp activities, appealing as the anti-Hp agents with low toxicity. Subsequently, some transition metal complexes with the better anti-Hp activities are also designed and synthesized. We believe that the development of new bismuth and transition metal complexes as anti-Hp agents may be a promising approach to increase the eradication rate of Hp infection. This review summarizes the most striking advances in the syntheses, crystal structures, and anti-Hp activities of bismuth and transition metal complexes, which attempt to not only reveal a correlation between their structural features and anti-Hp activities, but also offer the helpful guidance for the researchers in the future development of new bismuth and other important bio-metal complexes as the efficient anti-Hp agents.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117413"},"PeriodicalIF":2.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148719","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}

引用次数: 0

Reactions of [Ru3(CO)10(µ-dppe)] towards tetramethylthiourea and N,N′-diisopropylthiourea: Generation of tri- and tetraruthenium carbonyl clusters bearing bridging/chelating dppe, triply/quadruply bridging sulfido and aminocarbene ligands

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-20 DOI: 10.1016/j.poly.2025.117411

Md. Nazmul Huda , Md. Abdullah Al Mamun , Joyanta K. Saha , Vladimir N. Nesterov , Tareque S.M. Abedin , Shariff E. Kabir

Two new sulfur-capped ruthenium clusters, a triruthenium [Ru₃(CO)₇(μ-dppe)(μ₃-S)₂] (1) (41% yield) and a tetraruthenium [Ru₄(CO)₆(µ-CO)₂{η¹-C(NMe₂)₂}(κ²-dppe)(µ₄-S)₂] (2) (15% yield) were obtained from the reaction of dppe-bridged triruthenium cluster [Ru₃(CO)₁₀(μ-dppe)] [dppe = 1,2-bis(diphenylhosphino)ethane] with four equivalents of tetramethylthiourea in THF at reflux. A similar reaction with N,N′-diisopropylthiourea in the same solvent and temperature exclusively afforded 1. Cluster 1 comprises an open Ru₃S₂ core capped by two μ₃-sulfido ligands resulting from activation of the C–S bond of the thiourea ligand, and the dppe ligand bridges the open Ru….Ru edge occupying axial sites. Cluster 2 provides a unique example of a Ru₄S₂ skeleton with a square-planar arrangement of the four ruthenium atoms, two quadruply bridging sulfido ligands on opposite faces of the cluster, a terminally coordinated tetramethyldiaminocarbene ligand, formed by desulfurization of tetramethylthiourea ligand, a chelating dppe and two bridging carbonyl ligands on adjacent Ru–Ru vectors. The molecular structures of 1 and 2 have been determined by spectroscopic (IR, ¹H NMR, and ³¹P{¹H} NMR) data and single-crystal X-ray diffraction analysis. The bonding of these new compounds has been examined using DFT optimization and topological analysis using atoms in molecules (AIM) quantum theory.

{"title":"Reactions of [Ru3(CO)10(µ-dppe)] towards tetramethylthiourea and N,N′-diisopropylthiourea: Generation of tri- and tetraruthenium carbonyl clusters bearing bridging/chelating dppe, triply/quadruply bridging sulfido and aminocarbene ligands","authors":"Md. Nazmul Huda , Md. Abdullah Al Mamun , Joyanta K. Saha , Vladimir N. Nesterov , Tareque S.M. Abedin , Shariff E. Kabir","doi":"10.1016/j.poly.2025.117411","DOIUrl":"10.1016/j.poly.2025.117411","url":null,"abstract":"<div><div>Two new sulfur-capped ruthenium clusters, a triruthenium [Ru3(CO)7(μ-dppe)(μ3-S)2] (1) (41% yield) and a tetraruthenium [Ru4(CO)6(µ-CO)2{η1-C(NMe2)2}(κ2-dppe)(µ4-S)2] (2) (15% yield) were obtained from the reaction of dppe-bridged triruthenium cluster [Ru3(CO)10(μ-dppe)] [dppe = 1,2-bis(diphenylhosphino)ethane] with four equivalents of tetramethylthiourea in THF at reflux. A similar reaction with N,N′-diisopropylthiourea in the same solvent and temperature exclusively afforded 1. Cluster 1 comprises an open Ru3S2 core capped by two μ3-sulfido ligands resulting from activation of the C–S bond of the thiourea ligand, and the dppe ligand bridges the open Ru….Ru edge occupying axial sites. Cluster 2 provides a unique example of a Ru4S2 skeleton with a square-planar arrangement of the four ruthenium atoms, two quadruply bridging sulfido ligands on opposite faces of the cluster, a terminally coordinated tetramethyldiaminocarbene ligand, formed by desulfurization of tetramethylthiourea ligand, a chelating dppe and two bridging carbonyl ligands on adjacent Ru–Ru vectors. The molecular structures of 1 and 2 have been determined by spectroscopic (IR, 1H NMR, and 31P{1H} NMR) data and single-crystal X-ray diffraction analysis. The bonding of these new compounds has been examined using DFT optimization and topological analysis using atoms in molecules (AIM) quantum theory.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117411"},"PeriodicalIF":2.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147747","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}

引用次数: 0

Bonding and reactivity study of chalcogen adducts of N-heterocyclic Silylene and Germylene: Fisher-carbene like bond polarity in heavier main group adducts

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-20 DOI: 10.1016/j.poly.2025.117412

Linta Mary Jose , Susmita De

The chalcogen-stabilized N-heterocyclic carbenes, Imidazolin-2-chalcogenones (NHC=X, X = O, S, Se), represent an important class of stable compounds with wide applications in catalysis. However, the chalcogen-stabilized N-heterocyclic Silylenes and Germylenes (NHE=X, E = Si, Ge; X = O, S, Se), which could potentially lead to a new class of low valent compounds, are not yet isolated, while their Lewis-base-supported adducts are. Therefore, the nature of the Si/Ge-chalcogen (_NHEE = X) bond is investigated and compared to the _NHCC=X bond using quantum mechanical methods to elucidate the differences in the stability and reactivity. The NBO, AIM, and MO analyses suggest that the _NHEE=X bond in the heavier analogues exhibits a Fischer-carbene like bond polarity for the main group adduct, and the polarity decreases going down the group. The EDA-NOCV (Energy Decomposition Analysis combined with Natural Orbitals for Chemical Valence) analysis confirms that the bonding in NHE=X except for NHGe=Se can be best represented by considering one electron sharing and one donor–acceptor interaction between positively charged NHE fragment (_NHEE⁺) and negatively charged chalcogen, which confirms the polar nature of the E─X bond. On the other hand, the preference for the singlet electronic state is translated in double donor–acceptor interactions between two neutral fragments (NHGe and Se) in NHGe=Se. In addition, an in-plane hyperconjugative _NHEE ← X (π_parallel) interaction is also observed. Our analysis further confirms the preference for ammonia addition to the Silylene/Germylene centre, thus corroborating the experimentally reported reactivity of Lewis base stabilized NHE=X.

{"title":"Bonding and reactivity study of chalcogen adducts of N-heterocyclic Silylene and Germylene: Fisher-carbene like bond polarity in heavier main group adducts","authors":"Linta Mary Jose , Susmita De","doi":"10.1016/j.poly.2025.117412","DOIUrl":"10.1016/j.poly.2025.117412","url":null,"abstract":"<div><div>The chalcogen-stabilized N-heterocyclic carbenes, Imidazolin-2-chalcogenones (NHC=X, X = O, S, Se), represent an important class of stable compounds with wide applications in catalysis. However, the chalcogen-stabilized N-heterocyclic Silylenes and Germylenes (NHE=X, E = Si, Ge; X = O, S, Se), which could potentially lead to a new class of low valent compounds, are not yet isolated, while their Lewis-base-supported adducts are. Therefore, the nature of the Si/Ge-chalcogen (NHEE = X) bond is investigated and compared to the NHCC=X bond using quantum mechanical methods to elucidate the differences in the stability and reactivity. The NBO, AIM, and MO analyses suggest that the NHEE=X bond in the heavier analogues exhibits a Fischer-carbene like bond polarity for the main group adduct, and the polarity decreases going down the group. The EDA-NOCV (Energy Decomposition Analysis combined with Natural Orbitals for Chemical Valence) analysis confirms that the bonding in NHE=X except for NHGe=Se can be best represented by considering one electron sharing and one donor–acceptor interaction between positively charged NHE fragment (NHEE+) and negatively charged chalcogen, which confirms the polar nature of the E─X bond. On the other hand, the preference for the singlet electronic state is translated in double donor–acceptor interactions between two neutral fragments (NHGe and Se) in NHGe=Se. In addition, an in-plane hyperconjugative NHEE ← X (πparallel) interaction is also observed. Our analysis further confirms the preference for ammonia addition to the Silylene/Germylene centre, thus corroborating the experimentally reported reactivity of Lewis base stabilized NHE=X.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117412"},"PeriodicalIF":2.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147326","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}

引用次数: 0

Novel mixed-ligand metal complexes containing anisic acid/nicotinamide ligands. Their synthesis, structural characterization and biological applications

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-20 DOI: 10.1016/j.poly.2025.117410

Esra Çataldağ , Dursun Ali Köse , Gizem Özlük , Onur Şahin

In this study, five different p-methoxybenzoate (anisate)-nicotinamide complex compounds, whose central atoms are transition metal cations (Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺), were synthesized and their structural characterizations were investigated. In addition, the antibacterial and antifungal properties of the compounds against various biological derivatives were investigated by disk diffusion method. Elemental analysis, magnetic susceptibility, FTIR spectra, thermoanalytical TG-DTG/DTA analysis and single crystal X-ray diffraction methods were used to determine the structural characterizations of the compounds. It was determined that the complexes containing Co²⁺ and Ni²⁺ cations, whose single crystal structures were solved, were isostructured. It was suggested that the coordination properties of the other three coordination compounds centered on Mn²⁺, Cu²⁺ and Zn²⁺ were like the solved structures because of the similarity of thermal and spectroscopic analysis results. Due to the nature of the metal cation, it was predicted that only the Cu²⁺ complex was in fivefold coordination and the coordination was completed with two anisate anions, two neutral nicotinamide ligands and one crystal water. It was determined that the other four complex structures were in sixfold coordination and that they completed their coordination with one more crystal water, unlike the Cu²⁺ complex. It was also seen that the complex with the Co²⁺ central atom contained two hydrate waters, unlike the other complexes. The presence of water molecules in the coordination compounds and the thermal decomposition steps of the structures were determined by TG/DTA curves.

{"title":"Novel mixed-ligand metal complexes containing anisic acid/nicotinamide ligands. Their synthesis, structural characterization and biological applications","authors":"Esra Çataldağ , Dursun Ali Köse , Gizem Özlük , Onur Şahin","doi":"10.1016/j.poly.2025.117410","DOIUrl":"10.1016/j.poly.2025.117410","url":null,"abstract":"<div><div>In this study, five different p-methoxybenzoate (anisate)-nicotinamide complex compounds, whose central atoms are transition metal cations (Mn2+, Co2+, Ni2+, Cu2+ and Zn2+), were synthesized and their structural characterizations were investigated. In addition, the antibacterial and antifungal properties of the compounds against various biological derivatives were investigated by disk diffusion method. Elemental analysis, magnetic susceptibility, FTIR spectra, thermoanalytical TG-DTG/DTA analysis and single crystal X-ray diffraction methods were used to determine the structural characterizations of the compounds. It was determined that the complexes containing Co2+ and Ni2+ cations, whose single crystal structures were solved, were isostructured. It was suggested that the coordination properties of the other three coordination compounds centered on Mn2+, Cu2+ and Zn2+ were like the solved structures because of the similarity of thermal and spectroscopic analysis results. Due to the nature of the metal cation, it was predicted that only the Cu2+ complex was in fivefold coordination and the coordination was completed with two anisate anions, two neutral nicotinamide ligands and one crystal water. It was determined that the other four complex structures were in sixfold coordination and that they completed their coordination with one more crystal water, unlike the Cu2+ complex. It was also seen that the complex with the Co2+ central atom contained two hydrate waters, unlike the other complexes. The presence of water molecules in the coordination compounds and the thermal decomposition steps of the structures were determined by TG/DTA curves.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117410"},"PeriodicalIF":2.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148720","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}

引用次数: 0

Efficiently catalytic glycerol to solketal through acetalization over sulfated UiO-66

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-20 DOI: 10.1016/j.poly.2025.117407

Wu Wang , He Gong

Herein, a facile synthetic approach was developed to prepare sulfated UiO-66 (named as UiO-SO₃H-X, X represents the molar fraction of the sulfonated ligand). UiO-SO₃H-X were comprehensively characterized using powder X-ray diffraction (pXRD), Fourier Transform Infrared Spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), Thermal Gravimetric Analyzer (TGA), N₂ adsorption–desorption, Transmission Electron Microscope (TEM) analyses. The sulfonic acid groups were uniformly dispersed throughout the crystalline framework. Notably, UiO-SO₃H-30 exhibits superior catalytic activity and durability in the acetalization reaction of solketal from glycerol. Glycerol conversion of 79.6 % with a solketal selectivity of 99.5 % was achieved at 60 °C, while maintaining initial activity for 5 consecutive cycles. Meantime, UiO-SO₃H-30 possesses a maximum turnover frequency (TOF) of 272.3 h⁻¹ for per acid site, which is superior than most heterogeneous acid catalysts. This work supplies a feasible method to synthesize upstream by product of biodiesel, producing significant influence for biomass utilization in chemical industry fields.

{"title":"Efficiently catalytic glycerol to solketal through acetalization over sulfated UiO-66","authors":"Wu Wang , He Gong","doi":"10.1016/j.poly.2025.117407","DOIUrl":"10.1016/j.poly.2025.117407","url":null,"abstract":"<div><div>Herein, a facile synthetic approach was developed to prepare sulfated UiO-66 (named as UiO-SO3H-X, X represents the molar fraction of the sulfonated ligand). UiO-SO3H-X were comprehensively characterized using powder X-ray diffraction (pXRD), Fourier Transform Infrared Spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), Thermal Gravimetric Analyzer (TGA), N2 adsorption–desorption, Transmission Electron Microscope (TEM) analyses. The sulfonic acid groups were uniformly dispersed throughout the crystalline framework. Notably, UiO-SO3H-30 exhibits superior catalytic activity and durability in the acetalization reaction of solketal from glycerol. Glycerol conversion of 79.6 % with a solketal selectivity of 99.5 % was achieved at 60 °C, while maintaining initial activity for 5 consecutive cycles. Meantime, UiO-SO3H-30 possesses a maximum turnover frequency (TOF) of 272.3 h−1 for per acid site, which is superior than most heterogeneous acid catalysts. This work supplies a feasible method to synthesize upstream by product of biodiesel, producing significant influence for biomass utilization in chemical industry fields.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117407"},"PeriodicalIF":2.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148716","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}

引用次数: 0

Investigating the DNA binding properties of diruthenium complexes incorporating carboxylated chalcone ligands with phenyl, naphthyl or anthryl moieties

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-19 DOI: 10.1016/j.poly.2025.117409

Jiaxin Zou , Songyang Zhang , Bo Zhang , Peter P.F. Lee , Rakesh Ganguly , Yong Leng Kelvin Tan

Sixteen diruthenium sawhorse and cationic complexes with carboxylated chalcone ligands incorporating phenyl, naphthyl and anthryl moieties have been synthesized and characterized. The cationic complexes were found to be more soluble in aqueous medium than the neutral sawhorse compounds. DNA binding studies carried out for the cationic complexes indicate that the presence of the phenyl, naphthyl and anthryl units influenced the selectivity of the complexes towards quadruplex or duplex DNA.

引用次数: 0

Correlations in Cu-based chalcogenides for optical and transport performance in sustainable technologies: First-principles calculation

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-16 DOI: 10.1016/j.poly.2025.117388

M.M. Moharam , Muhammad Irfan , Sana Ullah Asif , Hesham M.H. Zakaly

Researchers have taken an interest in semiconductor chalcogenide compounds because of the wide variety of physical properties that these compounds exhibit. The study of the elastic, optical, and thermoelectric properties of Cu-based AlCu₃PbX₄ (X = S, Se, Te) chalcogenides has been conducted using the PBEsol-mBJ scheme within the framework of Density Functional Theory (DFT). The calculated band structure shows that both direct band gaps are semiconducting (1.0 eV–1.8 eV) as the valence band maximum (VBM) is primarily formed of Cu-d states. The conduction band minima (CBM) is primarily Al/Pb-s, p states. The optical and thermoelectric properties of AlCu₃PbX₄ (X = S, Se, Te) have been thoroughly examined using first-principles calculations. The dielectric function analysis reveals a static dielectric constant of 5.5–8.6, with significant peaks in the visible and ultraviolet regions. The refractive index varies between 2.0 and 2.8, while the absorption coefficient reaches a maximum of 180 cm⁻¹ in the UV range, indicating strong optical absorption. These materials exhibit high reflectivity (>40 %) at photon energies exceeding 4 eV and a plasmon energy loss peak near 13 eV. Zener anisotropy factor deviating from 1, indicates anisotropic elastic behavior, while Pugh’s ratio (B/G), which is less than 1.75 for these materials, further classifies them as brittle in nature. Thermoelectric investigations using Boltztrap show high Seebeck coefficients of 250–400 µV/K, power factors of 2.0 × 10¹⁰ to 8.0 × 10¹⁰ W/mK²s, and impressive dimensionless figure-of-merit (ZT) values of 0.1–1.1 at temperatures (∼800 K), demonstrating their potential for high-efficiency thermoelectric applications. These findings suggest that AlCu₃PbX₄ compounds are promising candidates for energy-efficient thermoelectric and optoelectronic devices.

{"title":"Correlations in Cu-based chalcogenides for optical and transport performance in sustainable technologies: First-principles calculation","authors":"M.M. Moharam , Muhammad Irfan , Sana Ullah Asif , Hesham M.H. Zakaly","doi":"10.1016/j.poly.2025.117388","DOIUrl":"10.1016/j.poly.2025.117388","url":null,"abstract":"<div><div>Researchers have taken an interest in semiconductor chalcogenide compounds because of the wide variety of physical properties that these compounds exhibit. The study of the elastic, optical, and thermoelectric properties of Cu-based AlCu3PbX4 (X = S, Se, Te) chalcogenides has been conducted using the PBEsol-mBJ scheme within the framework of Density Functional Theory (DFT). The calculated band structure shows that both direct band gaps are semiconducting (1.0 eV–1.8 eV) as the valence band maximum (VBM) is primarily formed of Cu-d states. The conduction band minima (CBM) is primarily Al/Pb-s, p states. The optical and thermoelectric properties of AlCu3PbX4 (X = S, Se, Te) have been thoroughly examined using first-principles calculations. The dielectric function analysis reveals a static dielectric constant of 5.5–8.6, with significant peaks in the visible and ultraviolet regions. The refractive index varies between 2.0 and 2.8, while the absorption coefficient reaches a maximum of 180 cm−1 in the UV range, indicating strong optical absorption. These materials exhibit high reflectivity (>40 %) at photon energies exceeding 4 eV and a plasmon energy loss peak near 13 eV. Zener anisotropy factor deviating from 1, indicates anisotropic elastic behavior, while Pugh’s ratio (B/G), which is less than 1.75 for these materials, further classifies them as brittle in nature. Thermoelectric investigations using Boltztrap show high Seebeck coefficients of 250–400 µV/K, power factors of 2.0 × 1010 to 8.0 × 1010 W/mK2s, and impressive dimensionless figure-of-merit (ZT) values of 0.1–1.1 at temperatures (∼800 K), demonstrating their potential for high-efficiency thermoelectric applications. These findings suggest that AlCu3PbX4 compounds are promising candidates for energy-efficient thermoelectric and optoelectronic devices.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117388"},"PeriodicalIF":2.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148713","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}

引用次数: 0

f-Element complexes with benzyl and cyclohexyl substituted trihydroborates

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-16 DOI: 10.1016/j.poly.2025.117408

Joshua C. Zgrabik, Peter A. Zacher III, Scott R. Daly

Actinide complexes containing the simplest borohydrides (BH₄)¹⁻ and (MeBH₃)¹⁻ can exhibit remarkably highly volatility, which creates unique hazards and handling challenges, especially when making measurements on solid samples under vacuum. Here we describe efforts to prepare new actinide borohydride complexes with attenuated volatility by adding bulkier benzyl (Bn) and cyclohexyl (Cy) substituents to boron. Reactions of ThCl₄, UI₃(thf)₄, and NdI₃ with the mixed alkali metal salt Li/K(BnBH₃)(thf)_n yielded Th(BnBH₃)₄(thf)₂, U(BnBH₃)₄(thf)₂, and K[Nd(BnBH₃)₄], respectively. Notable amongst these, the reaction with UI₃(thf)₄ proceeds via oxidation of U(III) to U(IV) despite the presence of reducing borohydride ligands. Similarly, reactions of the same metal halides with four equivalents of Li(CyBH₃)(Et₂O)_n yielded Th(CyBH₃)₄, U(CyBH₃)₄(thf)₂, and [Li(Et₂O)₃][Nd(CyBH₃)₄]. Single crystal X-ray diffraction studies of the M(BnBH₃)₄(thf)₂ complexes with M = Th and U confirmed their formulations. The complexes have approximate D_2d point group symmetry and adopt bicapped hexagonal antiprismatic coordination geometries with axial thf ligands and κ³-BnBH₃ ligands bound in the equatorial plane. K[Nd(BnBH₃)₄] and [Li(Et₂O)₃][Nd(CyBH₃)₄], which were prepared for comparison to U(III) complexes that were unsuccessfully targeted, were also structurally characterized to reveal complex anions with tetrahedral arrangements of trihydroborate ligands bound to Nd(III). Crystals obtained for Th(CyBH₃)₄ and U(CyBH₃)₄(thf)₂ were not suitable for XRD studies, but ¹H and ¹¹B NMR spectra were consistent with their formulations. Collectively, these complexes represent rare examples of structurally characterized f-element trihydroborate complexes with carbon substituents other than methyl.

{"title":"f-Element complexes with benzyl and cyclohexyl substituted trihydroborates","authors":"Joshua C. Zgrabik, Peter A. Zacher III, Scott R. Daly","doi":"10.1016/j.poly.2025.117408","DOIUrl":"10.1016/j.poly.2025.117408","url":null,"abstract":"<div><div>Actinide complexes containing the simplest borohydrides (BH4)1− and (MeBH3)1− can exhibit remarkably highly volatility, which creates unique hazards and handling challenges, especially when making measurements on solid samples under vacuum. Here we describe efforts to prepare new actinide borohydride complexes with attenuated volatility by adding bulkier benzyl (Bn) and cyclohexyl (Cy) substituents to boron. Reactions of ThCl4, UI3(thf)4, and NdI3 with the mixed alkali metal salt Li/K(BnBH3)(thf)n yielded Th(BnBH3)4(thf)2, U(BnBH3)4(thf)2, and K[Nd(BnBH3)4], respectively. Notable amongst these, the reaction with UI3(thf)4 proceeds via oxidation of U(III) to U(IV) despite the presence of reducing borohydride ligands. Similarly, reactions of the same metal halides with four equivalents of Li(CyBH3)(Et2O)n yielded Th(CyBH3)4, U(CyBH3)4(thf)2, and [Li(Et2O)3][Nd(CyBH3)4]. Single crystal X-ray diffraction studies of the M(BnBH3)4(thf)2 complexes with M = Th and U confirmed their formulations. The complexes have approximate D2d point group symmetry and adopt bicapped hexagonal antiprismatic coordination geometries with axial thf ligands and κ3-BnBH3 ligands bound in the equatorial plane. K[Nd(BnBH3)4] and [Li(Et2O)3][Nd(CyBH3)4], which were prepared for comparison to U(III) complexes that were unsuccessfully targeted, were also structurally characterized to reveal complex anions with tetrahedral arrangements of trihydroborate ligands bound to Nd(III). Crystals obtained for Th(CyBH3)4 and U(CyBH3)4(thf)2 were not suitable for XRD studies, but 1H and 11B NMR spectra were consistent with their formulations. Collectively, these complexes represent rare examples of structurally characterized f-element trihydroborate complexes with carbon substituents other than methyl.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117408"},"PeriodicalIF":2.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148715","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}

引用次数: 0

The synthesis, structure and solution and gas phase properties of complexes of scandium and lanthanide triflates with the phosphine oxide ligands PhP(O)(C2H4P(O)Ph2)2 and P(O)(C2H4P(O)Ph2)3

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-01-16 DOI: 10.1016/j.poly.2025.117395

Simon J. Coles , Ann P. Hunter , Sarah J. Fieldhouse , Anthony M.J. Lees , Laura J. McCormick McPherson , Andrew W.G. Platt

The synthesis and structures of complexes of PhP(O)(C₂H₄P(O)Ph₂)_2, L¹, and P(O)(C₂H₄P(O)Ph₂)₃, L², respectively, with scandium and lanthanide triflates are described. Single crystal x-ray structures of complexes of the octahedral [Sc(L¹)₃](OTf)₃, dodecahedral [Nd(OTf)(H₂O)(L¹)₂](OTf)₂ and [Ln(OTf)(H₂O)(L²)₂](OTf)₂ (Ln = La, Gd), and the dimeric [{Er(OTf)₂(H₂O)(μ–L²)}₂](OTf)₂ and [{Er(OTf)₂(EtOH)(μ–L²)}₂](OTf)₂, which have distorted pentagonal bipyramidal geometry around Er, have been determined. The solution properties of the complexes have been investigated by ¹⁹F and ³¹P NMR spectroscopy which show that the complexes of L¹ are fluxional with exchange of inequivalent coordinated Ph₂PO groups in solution. Complexes of L² show the same process and exchange between coordinated and pendant arms of the ligand. The stability in the gas phase has been investigated by electrospray mass spectrometry (ESMS) and tandem ESMS where, in addition to loss of triflate, L¹ and L², loss of diphenylphosphine oxide and Ph₂P(O)C₂H₄OSO₂CF₃ are shown to be significant decomposition pathways for complexes of both ligands. A brief study of the catalytic properties of a range of complexes shows that the alkenylation of 1,4-dimethoxybenzene with phenylacetylene in nitromethane does not occur at 80 °C for complexes of L¹ or L².

{"title":"The synthesis, structure and solution and gas phase properties of complexes of scandium and lanthanide triflates with the phosphine oxide ligands PhP(O)(C2H4P(O)Ph2)2 and P(O)(C2H4P(O)Ph2)3","authors":"Simon J. Coles , Ann P. Hunter , Sarah J. Fieldhouse , Anthony M.J. Lees , Laura J. McCormick McPherson , Andrew W.G. Platt","doi":"10.1016/j.poly.2025.117395","DOIUrl":"10.1016/j.poly.2025.117395","url":null,"abstract":"<div><div>The synthesis and structures of complexes of PhP(O)(C2H4P(O)Ph2)2, L1, and P(O)(C2H4P(O)Ph2)3, L2, respectively, with scandium and lanthanide triflates are described. Single crystal x-ray structures of complexes of the octahedral [Sc(L1)3](OTf)3, dodecahedral [Nd(OTf)(H2O)(L1)2](OTf)2 and [Ln(OTf)(H2O)(L2)2](OTf)2 (Ln = La, Gd), and the dimeric [{Er(OTf)2(H2O)(μ–L2)}2](OTf)2 and [{Er(OTf)2(EtOH)(μ–L2)}2](OTf)2, which have distorted pentagonal bipyramidal geometry around Er, have been determined. The solution properties of the complexes have been investigated by 19F and 31P NMR spectroscopy which show that the complexes of L1 are fluxional with exchange of inequivalent coordinated Ph2PO groups in solution. Complexes of L2 show the same process and exchange between coordinated and pendant arms of the ligand. The stability in the gas phase has been investigated by electrospray mass spectrometry (ESMS) and tandem ESMS where, in addition to loss of triflate, L1 and L2, loss of diphenylphosphine oxide and Ph2P(O)C2H4OSO2CF3 are shown to be significant decomposition pathways for complexes of both ligands. A brief study of the catalytic properties of a range of complexes shows that the alkenylation of 1,4-dimethoxybenzene with phenylacetylene in nitromethane does not occur at 80 °C for complexes of L1 or L2.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"269 ","pages":"Article 117395"},"PeriodicalIF":2.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143148717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0