Pub Date : 2025-02-13DOI: 10.1016/j.poly.2025.117448
Sergey A. Zdanovich , Elena Yu. Tyulyaeva , Vitaliy S. Sukharev , Mark V. Zaitsev , Svetlana V. Zaitseva
Binuclear μ-bridged macrocycle dimers have been attracting considerable attention because of their catalytic ability in organic substrates oxidation. This work focuses on the preparation and properties of novel µ-nitrido iron–manganese homo-/heteroleptic complexes bearing porphyrin and phthalocyanine ligands. The compounds are identified and studied using UV, IR, EPR spectroscopy, mass spectrometry, and electrochemistry techniques. Subjecting the complexes to tBuOOH in CH2Cl2 resulted in chemical generation of different high-valence species capable of decomposing β-carotene and peroxide at room temperature. The active reaction intermediates are rather stable to be identified using spectroscopic methods aiming at further establishing the reaction mechanism. The complexes composition is found to affect their redox properties and path of the studied substrate oxidation. The findings contribute to expanding the range of compounds with the controlled oxidizing capability to create active and durable catalysts.
{"title":"Novel µ-nitrido homo-/heteroleptic iron–manganese complexes as promising oxidants","authors":"Sergey A. Zdanovich , Elena Yu. Tyulyaeva , Vitaliy S. Sukharev , Mark V. Zaitsev , Svetlana V. Zaitseva","doi":"10.1016/j.poly.2025.117448","DOIUrl":"10.1016/j.poly.2025.117448","url":null,"abstract":"<div><div>Binuclear μ-bridged macrocycle dimers have been attracting considerable attention because of their catalytic ability in organic substrates oxidation. This work focuses on the preparation and properties of novel µ-nitrido iron–manganese homo-/heteroleptic complexes bearing porphyrin and phthalocyanine ligands. The compounds are identified and studied using UV, IR, EPR spectroscopy, mass spectrometry, and electrochemistry techniques. Subjecting the complexes to <em><sup>t</sup></em>BuOOH in CH<sub>2</sub>Cl<sub>2</sub> resulted in chemical generation of different high-valence species capable of decomposing β-carotene and peroxide at room temperature. The active reaction intermediates are rather stable to be identified using spectroscopic methods aiming at further establishing the reaction mechanism. The complexes composition is found to affect their redox properties and path of the studied substrate oxidation. The findings contribute to expanding the range of compounds with the controlled oxidizing capability to create active and durable catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117448"},"PeriodicalIF":2.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418947","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 : 2025-02-13DOI: 10.1016/j.poly.2025.117442
Han Liu , Xiao-Lin Liu , Hao Wang , Yang Liu , Xin-Tao Wu , Tian-Lu Sheng
To investigate how the electron-donating ability of the ligand influence the metal-to-metal charge transfer (MMCT) in mixed-valence (MV) systems, a series of asymmetric binuclear cyanido-bridged complexes CpMex(dppe)FeCNRu(bimpy)(PPh3)(NCCH3), N[PF6]2 (x = 1, 3, 4, 5; N = 1, 2, 3, 4; CpMe = methylcyclopentadiene; CpMe3 = 1, 2, 4-trimethyl-cyclopentadiene; CpMe4 = 1, 2, 3, 4-tetramethyl-cyclopentadienyl; CpMe5 = 1, 2, 3, 4, 5-pentamethyl-cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; bimpy = 2, 6-Bis(benzimidazol-2-yl)pyridine; PPh3 = triphenylphosphine), along with their one-electron oxidized products N[PF6]3 were synthesized and well characterized. In these MV systems, significant electronic interactions between the two metal centers were revealed by electrochemistry, crystallography, FTIR, UV–vis-NIR, and supported by the DFT calculations. The results showed that the MM’CT energy from the RuII to the FeIII increases as the electron-donating ability of the CpMeX ligands was enhanced with the addition of methyl substituents. Meanwhile, all the one-electron oxidized products N[PF6]3 belong to Class II systems.
{"title":"Influence of ligand donation on charge transfer properties of cyanido-bridged binuclear Fe-Ru complexes","authors":"Han Liu , Xiao-Lin Liu , Hao Wang , Yang Liu , Xin-Tao Wu , Tian-Lu Sheng","doi":"10.1016/j.poly.2025.117442","DOIUrl":"10.1016/j.poly.2025.117442","url":null,"abstract":"<div><div>To investigate how the electron-donating ability of the ligand influence the metal-to-metal charge transfer (MMCT) in mixed-valence (MV) systems, a series of asymmetric binuclear cyanido-bridged complexes CpMe<sub>x</sub>(dppe)FeCNRu(bimpy)(PPh<sub>3</sub>)(NCCH<sub>3</sub>), <strong>N[PF<sub>6</sub>]<sub>2</sub></strong> (x = 1, 3, 4, 5; N = <strong>1</strong>, <strong>2</strong>, <strong>3</strong>, <strong>4</strong>; CpMe = methylcyclopentadiene; CpMe<sub>3</sub> = 1, 2, 4-trimethyl-cyclopentadiene; CpMe<sub>4</sub> = 1, 2, 3, 4-tetramethyl-cyclopentadienyl; CpMe<sub>5</sub> = 1, 2, 3, 4, 5-pentamethyl-cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; bimpy = 2, 6-Bis(benzimidazol-2-yl)pyridine; PPh<sub>3</sub> = triphenylphosphine), along with their one-electron oxidized products <strong>N[PF<sub>6</sub>]<sub>3</sub></strong> were synthesized and well characterized. In these MV systems, significant electronic interactions between the two metal centers were revealed by electrochemistry, crystallography, FTIR, UV–vis-NIR, and supported by the DFT calculations. The results showed that the MM’CT energy from the Ru<sup>II</sup> to the Fe<sup>III</sup> increases as the electron-donating ability of the CpMe<sub>X</sub> ligands was enhanced with the addition of methyl substituents. Meanwhile, all the one-electron oxidized products <strong>N[PF<sub>6</sub>]<sub>3</sub></strong> belong to Class II systems.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117442"},"PeriodicalIF":2.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438273","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 : 2025-02-12DOI: 10.1016/j.poly.2025.117446
Shahid Iqbal , Firdous Bibi , Muhammad Jamshaid , Ambreen Kalsoom , Wedad A. Al-onazi , Mohamed S. Elshikh , Md Rezaul Karim , Ismail Hossain
In this current investigation, it deals with the synthesis of a highly effective Z-scheme visible light-driven Sm-Fe-doped LaNiO3/g-C3N4 hetero-structure photocatalyst for the efficient elimination of toxic environmental pollutants from wastewater. Pristine LaNiO3 nanoparticles (NP), samarium, and iron (Sm-Fe) doped LaNiO3 NP and their nanohybrid composite Sm-Fe doped LaNiO3/g-C3N4 with 15 % (g-C3N4) graphitic-carbon-nitride was prepared via facile glycerine-assisted hydrothermal and ultra-sonication approaches. The materials for their physico-chemical properties were characterized using SEM, TEM, P-XRD, FTIR, XPS, BET, I-V, VSM, PL, and UV–visible analysis. The morphological analysis revealed that the g-C3N4 sheets interact and buffer with Sm-Fe-doped LaNiO3 NP, forming larger, elongated aggregations having highly exposed surfaces, wider particle size distributions and possessing an average particle sizes 22–34 nm. Structural investigation demonstrated the single-phase rhombohedral LaNiO3 perovskite along with successful Sm and Fe cation doping. The Sm-Fe-doped LaNiO3/g-C3N4 nanohybrid materials exhibited excellent BET surface area (96.7 m2/g), a well-porous nature with average pore sizes in the 1.5–2.6 nm range, good saturation magnetization (2.204 10−3 Ms/emu), boosted electrical conductivity (1.09 102 Sm−1) and a narrow band gap (2.06 eV), which was credited to the Sm-Fe-doping and the combination of highly conducting g-C3N4 material. It was demonstrated that Sm-Fe-doped LaNiO3 NP were uniformly dispersed on g-C3N4 nanohybrids, forming an intimate interface with robust interaction between LaNiO3 and the g-C3N4, which promoted efficient charge mobility and separation, forming a Z-scheme photocatalytic system. The photo-degradation investigation of the newly synthesized photo-catalyst was tested against methylene blue (MB) dye and moxifloxacin (MOX) drug under solar-light irradiation. The Sm-Fe-doped LaNiO3/g-C3N4 nanohybrid photocatalyst exhibited excellent removal of MB dye (97.8 %) and MOX (96.4 %) in only 55 min. This superb removal proficiency of MB dye and MOX by Sm-Fe-doped LaNiO3/g-C3N4 nanohybrid was attributed to its improved magnetic, good electrical, well-porosity, and excellent optical absorption characteristics, which make the Sm-Fe-doped LaNiO3/g-C3N4 nanohybrid as a novel materials for removing toxic environmental pollutants.
{"title":"Z-scheme design of hydrothermally synthesized Sm-Fe-doped LaNiO3/g-C3N4 heterostructure photo-catalyst for the efficient elimination of methylene blue & moxifloxacin pollutants","authors":"Shahid Iqbal , Firdous Bibi , Muhammad Jamshaid , Ambreen Kalsoom , Wedad A. Al-onazi , Mohamed S. Elshikh , Md Rezaul Karim , Ismail Hossain","doi":"10.1016/j.poly.2025.117446","DOIUrl":"10.1016/j.poly.2025.117446","url":null,"abstract":"<div><div>In this current investigation, it deals with the synthesis of a highly effective Z-scheme visible light-driven Sm-Fe-doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> hetero-structure photocatalyst for the efficient elimination of toxic environmental pollutants from wastewater. Pristine LaNiO<sub>3</sub> nanoparticles (NP), samarium, and iron (Sm-Fe) doped LaNiO<sub>3</sub> NP and their nanohybrid composite Sm-Fe doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> with 15 % (g-C<sub>3</sub>N<sub>4</sub>) graphitic-carbon-nitride was prepared via facile glycerine-assisted hydrothermal and ultra-sonication approaches. The materials for their physico-chemical properties were characterized using SEM, TEM, P-XRD, FTIR, XPS, BET, I-V, VSM, PL, and UV–visible analysis. The morphological analysis revealed that the g-C<sub>3</sub>N<sub>4</sub> sheets interact and buffer with Sm-Fe-doped LaNiO<sub>3</sub> NP, forming larger, elongated aggregations having highly exposed surfaces, wider particle size distributions and possessing an average particle sizes 22–34 nm. Structural investigation demonstrated the single-phase rhombohedral LaNiO<sub>3</sub> perovskite along with successful Sm and Fe cation doping. The Sm-Fe-doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> nanohybrid materials exhibited excellent BET surface area (96.7 m<sup>2</sup>/g), a well-porous nature with average pore sizes in the 1.5–2.6 nm range, good saturation magnetization (2.204 <span><math><mo>×</mo></math></span> 10<sup>−3</sup> Ms/emu), boosted electrical conductivity (1.09 <span><math><mo>×</mo></math></span> 10<sup>2</sup> Sm<sup>−1</sup>) and a narrow band gap (2.06 eV), which was credited to the Sm-Fe-doping and the combination of highly conducting g-C<sub>3</sub>N<sub>4</sub> material. It was demonstrated that Sm-Fe-doped LaNiO<sub>3</sub> NP were uniformly dispersed on g-C<sub>3</sub>N<sub>4</sub> nanohybrids, forming an intimate interface with robust interaction between LaNiO<sub>3</sub> and the g-C<sub>3</sub>N<sub>4</sub>, which promoted efficient charge mobility and separation, forming a Z-scheme photocatalytic system. The photo-degradation investigation of the newly synthesized photo-catalyst was tested against methylene blue (MB) dye and moxifloxacin (MOX) drug under solar-light irradiation. The Sm-Fe-doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> nanohybrid photocatalyst exhibited excellent removal of MB dye (97.8 %) and MOX (96.4 %) in only 55 min. This superb removal proficiency of MB dye and MOX by Sm-Fe-doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> nanohybrid was attributed to its improved magnetic, good electrical, well-porosity, and excellent optical absorption characteristics, which make the Sm-Fe-doped LaNiO<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> nanohybrid as a novel materials for removing toxic environmental pollutants.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117446"},"PeriodicalIF":2.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419057","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}
Zinc(II) phthalocyanines containing eight tert-butylphenoxy and tert-butylcarbazole groups at the molecule periphery (ZnPc(tBuPhO)8 and ZnPc(Carb)8, respectively) were obtained with about 20 % yield by the DBU activated phthalonitrile tetramerization in pentanol and dry quinoline, respectively. Their structure was confirmed using MALDI-TOF mass spectrometry, IR, 1H/13C NMR, and electronic absorption/fluorescence spectroscopy. The ZnPc(tBuPhO)8/ZnPc(Carb)8/H2Pc(tBuPhO)8 photophysical parameters, including the Q-band wavelength, fluorescence/singlet oxygen quantum yields, fluorescence lifetime, and radiative/non-radiative transition constant in organic solvents, were established. The presence of ZnPc(tBuPhO)8 and ZnPc(Carb)8 long-life excited states is confirmed by the fs-TA data. The peripheral carbazole substitution decreases slightly both the fluorescence quantum yield and fluorescence lifetime (by ∼0.6 ns) relative to that for ZnPc(tBuPhO)8, but simultaneously increases the possibility of singlet oxygen generation. The formation of the H2Pc(tBuPhO)8 proton transfer complex in dimethylformamide leading to the increase in singlet oxygen yield more than 3 times was established. Attractive photophysical parameters, non-aggregated state in solutions, and the bathochromically located Q absorption band allow us to consider ZnPc(Carb)8 as a promising photosensitizer.
{"title":"Soluble peripherally tert-butylphenoxy/tert-butylcarbazole substituted zinc phthalocyanines and their photophysical properties","authors":"E.N. Ovchenkova, N.G. Bichan, M.S. Gruzdev, V.A. Mozgova, U.V. Chervonova, T.N. Lomova","doi":"10.1016/j.poly.2025.117447","DOIUrl":"10.1016/j.poly.2025.117447","url":null,"abstract":"<div><div>Zinc(II) phthalocyanines containing eight <em>tert</em>-butylphenoxy and <em>tert</em>-butylcarbazole groups at the molecule periphery (ZnPc(<em><sup>t</sup></em>BuPhO)<sub>8</sub> and ZnPc(Carb)<sub>8</sub>, respectively) were obtained with about 20 % yield by the DBU activated phthalonitrile tetramerization in pentanol and dry quinoline, respectively. Their structure was confirmed using MALDI-TOF mass spectrometry, IR, <sup>1</sup>H/<sup>13</sup>C NMR, and electronic absorption/fluorescence spectroscopy. The ZnPc(<em><sup>t</sup></em>BuPhO)<sub>8</sub>/ZnPc(Carb)<sub>8</sub>/H<sub>2</sub>Pc(<em><sup>t</sup></em>BuPhO)<sub>8</sub> photophysical parameters, including the Q-band wavelength, fluorescence/singlet oxygen quantum yields, fluorescence lifetime, and radiative/non-radiative transition constant in organic solvents, were established. The presence of ZnPc(<em><sup>t</sup></em>BuPhO)<sub>8</sub> and ZnPc(Carb)<sub>8</sub> long-life excited states is confirmed by the fs-TA data. The peripheral carbazole substitution decreases slightly both the fluorescence quantum yield and fluorescence lifetime (by ∼0.6 ns) relative to that for ZnPc(<em><sup>t</sup></em>BuPhO)<sub>8</sub>, but simultaneously increases the possibility of singlet oxygen generation. The formation of the H<sub>2</sub>Pc(<em><sup>t</sup></em>BuPhO)<sub>8</sub> proton transfer complex in dimethylformamide leading to the increase in singlet oxygen yield more than 3 times was established. Attractive photophysical parameters, non-aggregated state in solutions, and the bathochromically located Q absorption band allow us to consider ZnPc(Carb)<sub>8</sub> as a promising photosensitizer.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117447"},"PeriodicalIF":2.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419056","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 : 2025-02-08DOI: 10.1016/j.poly.2025.117441
Mohamed Shaker S. Adam , Zakaria S. Bakhuraisa , Mustafa J. Abdelmageed Abualreish , Ahmed Desoky M. Mohamad , Mamdouh A. Mohamed
Considering a facile synthesis and high coordination ability of substituted imines, a condensation reaction between 2-aminobenzenethiol and thiophene-2-carbaldehyde produced an interesting derivative of the thiophenyl imine ligand (HLSNS). The coordination feature of HLSNS with Mn(II) ions was studied in 1 and 2: 1 M ratios, leading to the formation of two different structural complexes, MnLSNSCl and Mn(LSNS)2, respectively. Their chemical structures were validated by several suitable techniques, covering also the micro-elemental analyses, thermogravimetric evaluation, magnetic properties, and conductivity behaviors. Biologically, the inhibitory action of HLSNS (the free ligand) and its Mn(II)-chelating reagents on the growth power of three common bacterial and fungal strains, beside three established human cancer cell lines, were evaluated in relation to the presented Mn(II) ion and the structural influences of MnLSNSCl and Mn(LSNS)2 compared to their free ligand (HLSNS). The antimicrobial and anticancer behavior was estimated based on the measured inhibitory zone (mm) and the half-effective inhibitory concentrations (IC50, mM). Discovering the pivotal influence of Mn(II) ions and their ratios in the two chelates on the binding strength to the calf thymus DNA (ct-DNA), which reported by the alterations in viscosity and spectrophotometric properties of DNA. The ct-DNA interaction strength was built on the values of binding constants, Gibb’s free energy, and chromism modes, confirming also the interaction modes. For the catalytic potential testing, both MnLSNSCl and Mn(LSNS)2 were employed for the oxidative progressing of benzyl alcohol using hydrogen peroxide in a homogenous phase at 80 °C. Both catalysts exhibited superior catalytic oxidative activity. The yield percentage of selective benzaldehyde using MnLSNSCl and Mn(LSNS)2 was 90 % after 4 h, and 84 % after 5 h, respectively. The discrepancy in the optimum activity for both catalysts pertained to the differences in their molecular structures, which helped to assume a convenient mechanism.
{"title":"Manganese(II) complexes of thiophenyl imino-ligand with synergistic behavior in biological systems, ct-DNA interactions, and catalytic oxidative performance of benzyl alcohol","authors":"Mohamed Shaker S. Adam , Zakaria S. Bakhuraisa , Mustafa J. Abdelmageed Abualreish , Ahmed Desoky M. Mohamad , Mamdouh A. Mohamed","doi":"10.1016/j.poly.2025.117441","DOIUrl":"10.1016/j.poly.2025.117441","url":null,"abstract":"<div><div>Considering a facile synthesis and high coordination ability of substituted imines, a condensation reaction between 2-aminobenzenethiol and thiophene-2-carbaldehyde produced an interesting derivative of the thiophenyl imine ligand (HLSNS). The coordination feature of HLSNS with Mn(II) ions was studied in 1 and 2: 1 M ratios, leading to the formation of two different structural complexes, MnLSNSCl and Mn(LSNS)<sub>2</sub>, respectively. Their chemical structures were validated by several suitable techniques, covering also the micro-elemental analyses, thermogravimetric evaluation, magnetic properties, and conductivity behaviors. Biologically, the inhibitory action of HLSNS (the free ligand) and its Mn(II)-chelating reagents on the growth power of three common bacterial and fungal strains, beside three established human cancer cell lines, were evaluated in relation to the presented Mn(II) ion and the structural influences of MnLSNSCl and Mn(LSNS)<sub>2</sub> compared to their free ligand (HLSNS). The antimicrobial and anticancer behavior was estimated based on the measured inhibitory zone (mm) and the half-effective inhibitory concentrations (<em>IC</em><sub>50</sub>, mM). Discovering the pivotal influence of Mn(II) ions and their ratios in the two chelates on the binding strength to the calf thymus DNA (ct-DNA), which reported by the alterations in viscosity and spectrophotometric properties of DNA. The ct-DNA interaction strength was built on the values of binding constants, Gibb’s free energy, and chromism modes, confirming also the interaction modes. For the catalytic potential testing, both MnLSNSCl and Mn(LSNS)<sub>2</sub> were employed for the oxidative progressing of benzyl alcohol using hydrogen peroxide in a homogenous phase at 80 °C. Both catalysts exhibited superior catalytic oxidative activity. The yield percentage of selective benzaldehyde using MnLSNSCl and Mn(LSNS)<sub>2</sub> was 90 % after 4 h, and 84 % after 5 h, respectively. The discrepancy in the optimum activity for both catalysts pertained to the differences in their molecular structures, which helped to assume a convenient mechanism.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117441"},"PeriodicalIF":2.4,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394363","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 : 2025-02-07DOI: 10.1016/j.poly.2025.117444
Guo-Ling Zhao , Bo Kong , Zhi-Guo Wang , Xiu-Fang Mo , Xiao-Yi Yi
Treatment of pyrrole-cyclometalated IrIII starting [IrIII(K2C,N-dpp)(H)(Cl)(PPh3)2] (Hdpp = 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine) and [IrIIICp*Cl2]2 in the presence of base affords binuclear IrIII–IrIII complex [IrIII (H)(Cl)(PPh3)2(μ-dpp)IrIIICp*(Cl)] (1). The structural analysis of 1 displays two IrIII centers are linked by dpp2− ligand with novel μ-(K2C,N,K2N′,N″) coordination mode. The catalytic performance of 1 for formic acid dehydrogenation in water and CO2 hydrogenation is explored.
{"title":"Synthesis, characterization and catalytic properties of binuclear IrIII–IrIII complex containing pyridylpyrrole ligand","authors":"Guo-Ling Zhao , Bo Kong , Zhi-Guo Wang , Xiu-Fang Mo , Xiao-Yi Yi","doi":"10.1016/j.poly.2025.117444","DOIUrl":"10.1016/j.poly.2025.117444","url":null,"abstract":"<div><div>Treatment of pyrrole-cyclometalated Ir<sup>III</sup> starting [Ir<sup>III</sup>(<em>K</em><sup>2</sup><sub>C,</sub><em><sub>N</sub></em>-dpp)(H)(Cl)(PPh<sub>3</sub>)<sub>2</sub>] (Hdpp = 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine) and [Ir<sup>III</sup>Cp*Cl<sub>2</sub>]<sub>2</sub> in the presence of base affords binuclear Ir<sup>III</sup>–Ir<sup>III</sup> complex [Ir<sup>III</sup> (H)(Cl)(PPh<sub>3</sub>)<sub>2</sub>(μ-dpp)Ir<sup>III</sup>Cp*(Cl)] (<strong>1</strong>). The structural analysis of <strong>1</strong> displays two Ir<sup>III</sup> centers are linked by dpp<sup>2−</sup> ligand with novel μ-(<em>K</em><sup>2</sup><sub>C,N</sub>,<em>K</em><sup>2</sup><sub>N′,N″</sub>) coordination mode. The catalytic performance of <strong>1</strong> for formic acid dehydrogenation in water and CO<sub>2</sub> hydrogenation is explored.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117444"},"PeriodicalIF":2.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386586","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}
Three new Ag(I) coordination compounds, namely, (imH)2[Ag2(μ-Hssal)2(H2O)2] (1), {(2mimH)2[Ag2(μ3-Hssal)2(H2O)2]}n (2) and [Ag2(µ4-Hssal)(dmim)2]n (3) with 5-sulfosalicylic acid (H3ssal) and varying imidazole derivatives (imidazole (im), 2-methylimidazole (2mim), 1,2-dimethylimidazole (dmim)) were synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis, and single crystal X-ray diffraction techniques. While imidazole and 2-methylimidazole act as counter ions outside the coordination sphere as cations by undergoing proton transfer in complexes 1 and 2, 1,2-dimethylimidazole serves as a ligand in complex 3. Complex 1 is a binuclear compound while complex 2 is two-dimensional (2D) coordination polymer, and complex 3 is one-dimensional (1D) coordination polymer. The complexes 1–3 exhibite ligand-supported argentophilic Ag⋯Ag interactions. The luminescent properties of the complexes are also discussed.
{"title":"Synthesis, characterization and luminescent properties of silver(I) complexes with 5-sulfosalicylic acid and imidazole derivatives","authors":"Eda Çavuş Kaya , Figen Arslan Biçer , Ertan Şahin , Okan Zafer Yeşilel","doi":"10.1016/j.poly.2025.117443","DOIUrl":"10.1016/j.poly.2025.117443","url":null,"abstract":"<div><div>Three new Ag(I) coordination compounds, namely, (imH)<sub>2</sub>[Ag<sub>2</sub>(μ-Hssal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<strong>1</strong>), {(2mimH)<sub>2</sub>[Ag<sub>2</sub>(μ<sub>3</sub>-Hssal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]}<sub>n</sub> (<strong>2</strong>) and [Ag<sub>2</sub>(µ<sub>4</sub>-Hssal)(dmim)<sub>2</sub>]<sub>n</sub> (<strong>3</strong>) with 5-sulfosalicylic acid (H<sub>3</sub>ssal) and varying imidazole derivatives (imidazole (im), 2-methylimidazole (2mim), 1,2-dimethylimidazole (dmim)) were synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis, and single crystal X-ray diffraction techniques. While imidazole and 2-methylimidazole act as counter ions outside the coordination sphere as cations by undergoing proton transfer in complexes <strong>1</strong> and <strong>2</strong>, 1,2-dimethylimidazole serves as a ligand in complex <strong>3</strong>. Complex <strong>1</strong> is a binuclear compound while complex <strong>2</strong> is two-dimensional (2D) coordination polymer, and complex <strong>3</strong> is one-dimensional (1D) coordination polymer. The complexes <strong>1–3</strong> exhibite ligand-supported argentophilic Ag⋯Ag interactions. The luminescent properties of the complexes are also discussed.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117443"},"PeriodicalIF":2.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403176","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 : 2025-02-06DOI: 10.1016/j.poly.2025.117428
Aditya L. Shinde , Priyanka Velmurugan , Akash K. Sahoo , Shanmugam Revathi , Manickaraj Meena , Preethi Raja , Moris S. Eisen , Tapas Ghatak
Over the last hundred years, significant progress has been made in the chemistry of organo-f complexes, enhancing our understanding of their reactivity in both stoichiometric and catalytic processes. In the last three decades, there has been a significant rise in interest surrounding the electrophilic d0/fn chemistry of organo-f element complexes, attributable to their distinctive structure–reactivity relationships and remarkable efficacy in homogeneous catalysis. The influence of ligand design, encompassing electronic and steric considerations, on the catalytic efficacy of organo-f-complexes in diverse organic reactions is now broadly acknowledged. Notable progress in actinide chemistry has underscored their unique efficacy compared to lanthanides and transition metals. The stability of low-valent actinide complexes and the function of 5f orbitals in bonding and reactivity are, nevertheless, issues that continue to be extensively debated. Although actinides may share certain characteristics with transition metals in their chemical behaviors, they frequently reveal complementary or even enhanced reactivity. The increasing number of records in the Cambridge database highlights their escalating significance, facilitating more advanced chemical designs. The conventional view of actinide complexes as highly oxophilic has been limited by catalytic poisoning, which has restricted their use in oxygen-related processes. As a result, applications for these compounds have mostly found usage in cyclic ester polymerization, small-molecule activation, and hydroelementation. This review presents a comprehensive update on the synthesis, characteristics, and applications of important organoactinide complexes in organic processes. In conclusion, we present our Quo Vadis perspective, posing critical inquiries and articulating our insights regarding the future trends and advancements in this domain.
{"title":"Chemistry of uranium and thorium complexes towards challenging transformation: A recent trends","authors":"Aditya L. Shinde , Priyanka Velmurugan , Akash K. Sahoo , Shanmugam Revathi , Manickaraj Meena , Preethi Raja , Moris S. Eisen , Tapas Ghatak","doi":"10.1016/j.poly.2025.117428","DOIUrl":"10.1016/j.poly.2025.117428","url":null,"abstract":"<div><div>Over the last hundred years, significant progress has been made in the chemistry of organo-f complexes, enhancing our understanding of their reactivity in both stoichiometric and catalytic processes. In the last three decades, there has been a significant rise in interest surrounding the electrophilic d<sup>0</sup>/f<em><sup>n</sup></em> chemistry of organo-f element complexes, attributable to their distinctive structure–reactivity relationships and remarkable efficacy in homogeneous catalysis. The influence of ligand design, encompassing electronic and steric considerations, on the catalytic efficacy of organo-f-complexes in diverse organic reactions is now broadly acknowledged. Notable progress in actinide chemistry has underscored their unique efficacy compared to lanthanides and transition metals. The stability of low-valent actinide complexes and the function of 5f orbitals in bonding and reactivity are, nevertheless, issues that continue to be extensively debated. Although actinides may share certain characteristics with transition metals in their chemical behaviors, they frequently reveal complementary or even enhanced reactivity. The increasing number of records in the Cambridge database highlights their escalating significance, facilitating more advanced chemical designs. The conventional view of actinide complexes as highly oxophilic has been limited by catalytic poisoning, which has restricted their use in oxygen-related processes. As a result, applications for these compounds have mostly found usage in cyclic ester polymerization, small-molecule activation, and hydroelementation. This review presents a comprehensive update on the synthesis, characteristics, and applications of important organoactinide complexes in organic processes. In conclusion, we present our Quo Vadis perspective, posing critical inquiries and articulating our insights regarding the future trends and advancements in this domain.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117428"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394364","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 : 2025-02-06DOI: 10.1016/j.poly.2025.117429
Ali Rahmatpour , Mozhgan Amiri Baramkohi
The stability of crosslinked polyacrylamide and its ability to be modified for use in a variety of applications make it an excellent support material in heterogeneous systems. Herein, we report a novel catalyst derived from copper(I)-Schiff base complex and its immobilization into crosslinked polyacrylamide which was synthesized by a two-step process, followed by the fixation of copper(I) (CPAMSL@CuI). Various techniques were used to characterize the developed polymeric copper(I) catalyst.These methods included FTIR, ICP, DR-UV–vis., FTIR, XRD, FE-SEM, EDAX, TEM, TG/DTGA, and elemental analysis. The CPAM anchored copper(I) Schiff base complex demonstrated remarkably high catalytic activity in heterogeneous three-component click reactions of alkyl or benzyl halides, sodium azide, and terminal alkynes in water at room temperature with a low catalyst loading without adding any additives yielding 1,4-disubstituted 1,2,3-triazoles without generating any waste. Furthermore, the newly developed polymeric copper(I) catalyst could be recovered and reused six consecutive times without significantly reducing the reaction yield.
{"title":"Crosslinked polyacrylamide stabilized Cu(I) catalyst for efficient synthesis of 1,2,3-triazoles via click reactions","authors":"Ali Rahmatpour , Mozhgan Amiri Baramkohi","doi":"10.1016/j.poly.2025.117429","DOIUrl":"10.1016/j.poly.2025.117429","url":null,"abstract":"<div><div>The stability of crosslinked polyacrylamide and its ability to be modified for use in a variety of applications make it an excellent support material in heterogeneous systems. Herein, we report a novel catalyst derived from copper(I)-Schiff base complex and its immobilization into crosslinked polyacrylamide which was synthesized by a two-step process, followed by the fixation of copper(I) (CPAM<sub>SL</sub>@CuI). Various techniques were used to characterize the developed polymeric copper(I) catalyst.These methods included FTIR, ICP, DR-UV–vis., FTIR, XRD, FE-SEM, EDAX, TEM, TG/DTGA, and elemental analysis. The CPAM anchored copper(I) Schiff base complex demonstrated remarkably high catalytic activity in heterogeneous three-component click reactions of alkyl or benzyl halides, sodium azide, and terminal alkynes in water at room temperature with a low catalyst loading without adding any additives yielding 1,4-disubstituted 1,2,3-triazoles without generating any waste. Furthermore, the newly developed polymeric copper(I) catalyst could be recovered and reused six consecutive times without significantly reducing the reaction yield.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117429"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386691","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 : 2025-02-06DOI: 10.1016/j.poly.2025.117438
Sampat R. Shingda , Pranali H. Hadole , Hemant M. Alone , Kailas A. More , Anirudhha Mondal , Mohd Afzal , Ajay K. Potbhare , Sudip Mondal , Nilesh V. Gandhare
Green fabrication of nanocatalyst have been used in numerous organic reactions, due to its admirable catalytical, electrical, and mechanical properties. Especially, phyto-fabrication of carbon supported nanocatalyst achieved exceptional yield with small amount of catalyst loading in organic transformations, this unique nature of catalyst based on reactivity and renewability makes this material as an efficient, outstanding, and ecofriendly nanocatalyst. In the present study, ZnFe2O4@AC nanocomposites (NCs) were synthesized by co-precipitation method using leaves extract of Careya arborea. Moreover, synthesized ZnFe2O4@AC NCs were characterized by XRD, EDS, FE-SEM and HR-TEM. The XRD reveals cubic phase with high crystallinity. While, EDS analysis confirmed elemental purity of the ZnFe2O4@AC NCs and showed the carbon blending. However, HR-TEM images shown the cubic shape with an average size in the range of 18–22 nm. The obtained ZnFe2O4@AC NCs shows catalytic properties, which is applicable for organic transformation of derivatives of Quinazolin-4(1H)-one. These Quinazolin-4(1H)-one derivatives have been accomplished with single step reaction between aromatic aldehydes and 2-aminobenzamide at room temperature. Different aromatic aldehydes substrates were used for the preparation of Quinazolin-4(1H)-one derivatives. The spectroscopic data of FT-IR, 1H NMR and 13C NMR authenticates the formation of Quinazolin-4(1H)-one derivatives. Synthetic data of derivatives demonstrated that 20 mg of catalyst loading achieved remarkable 96 % yield in ethanol. The outcomes of the prepared derivatives confirm the purity of the organic compound, which offering protocol for organic transformation have some potential features such as a simple procedure, short reaction time, mild reaction conditions, easy workup, and high yield of products.
{"title":"Phyto-fabrication and characterization of ZnFe2O4@AC nanocomposite catalyst via green pathway and its application for the synthesis of some Quinazolin-4(1H)-one derivatives","authors":"Sampat R. Shingda , Pranali H. Hadole , Hemant M. Alone , Kailas A. More , Anirudhha Mondal , Mohd Afzal , Ajay K. Potbhare , Sudip Mondal , Nilesh V. Gandhare","doi":"10.1016/j.poly.2025.117438","DOIUrl":"10.1016/j.poly.2025.117438","url":null,"abstract":"<div><div>Green fabrication of nanocatalyst have been used in numerous organic reactions, due to its admirable catalytical, electrical, and mechanical properties. Especially, phyto-fabrication of carbon supported nanocatalyst achieved exceptional yield with small amount of catalyst loading in organic transformations, this unique nature of catalyst based on reactivity and renewability makes this material as an efficient, outstanding, and ecofriendly nanocatalyst. In the present study, ZnFe<sub>2</sub>O<sub>4</sub>@AC nanocomposites (NCs) were synthesized by co-precipitation method using leaves extract of <em>Careya arborea.</em> Moreover, synthesized ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs were characterized by XRD, EDS, FE-SEM and HR-TEM. The XRD reveals <em>cubic</em> phase with high crystallinity. While, EDS analysis confirmed elemental purity of the ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs and showed the carbon blending. However, HR-TEM images shown the <em>cubic</em> shape with an average size in the range of 18–22 nm. The obtained ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs shows catalytic properties, which is applicable for organic transformation of derivatives of Quinazolin-4(1H)-one. These Quinazolin-4(1H)-one derivatives have been accomplished with single step reaction between aromatic aldehydes and 2-aminobenzamide at room temperature. Different aromatic aldehydes substrates were used for the preparation of Quinazolin-4(1H)-one derivatives. The spectroscopic data of FT-IR, <sup>1</sup>H NMR and <sup>13</sup>C NMR authenticates the formation of Quinazolin-4(1H)-one derivatives. Synthetic data of derivatives demonstrated that 20 mg of catalyst loading achieved remarkable 96 % yield in ethanol. The outcomes of the prepared derivatives confirm the purity of the organic compound, which offering protocol for organic transformation have some potential features such as a simple procedure, short reaction time, mild reaction conditions, easy workup, and high yield of products.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117438"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419055","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}