William Daly,David J Otway,Ian M Povey,Martyn E Pemble
Molecular engineering of nine closely related copper(II) N,N-disubstituted-N'-acylthiourea complexes (single source precursors containing pre-organised Cu-S bonding motifs) has enabled systematic optimisation of their volatilisation behaviour and thermal stability. The influence of ligand substituents, steric branching, and solid-state geometry on precursor performance was examined. All complexes are monomeric and exhibit high thermal stability, with tuneable volatility arising from structural modifications to the acylthiourea backbone. Based on thermal and vapour pressure analysis, the most promising candidates were selected for proof-of-concept solvent free Chemical Vapour Deposition (CVD), representing the first use of this ligand class in a purely thermal deposition process; previous reports employed only aerosol-assisted CVD. Under these conditions the precursors yielded a copper rich digenite (Cu1.8S) nanocrystalline material; with a minor covellite (CuS) contribution observed, likely arising from an incompletely converted surface layer. Vapour pressure measurements demonstrate that, through appropriate ligand design, an equilibrium vapour pressure of ≈0.1 Torr can be achieved without compromising precursor stability. These results highlight N,N-disubstituted-N'-acylthiourea complexes as a versatile and tuneable platform for single-source precursor development.
{"title":"Investigation into the viability of N,N-disubstituted-N'-acylthiourea copper(II) precursors for thermal deposition without the use of solvents and the affect precursor geometry has on the deposited composites.","authors":"William Daly,David J Otway,Ian M Povey,Martyn E Pemble","doi":"10.1039/d4dt03482a","DOIUrl":"https://doi.org/10.1039/d4dt03482a","url":null,"abstract":"Molecular engineering of nine closely related copper(II) N,N-disubstituted-N'-acylthiourea complexes (single source precursors containing pre-organised Cu-S bonding motifs) has enabled systematic optimisation of their volatilisation behaviour and thermal stability. The influence of ligand substituents, steric branching, and solid-state geometry on precursor performance was examined. All complexes are monomeric and exhibit high thermal stability, with tuneable volatility arising from structural modifications to the acylthiourea backbone. Based on thermal and vapour pressure analysis, the most promising candidates were selected for proof-of-concept solvent free Chemical Vapour Deposition (CVD), representing the first use of this ligand class in a purely thermal deposition process; previous reports employed only aerosol-assisted CVD. Under these conditions the precursors yielded a copper rich digenite (Cu1.8S) nanocrystalline material; with a minor covellite (CuS) contribution observed, likely arising from an incompletely converted surface layer. Vapour pressure measurements demonstrate that, through appropriate ligand design, an equilibrium vapour pressure of ≈0.1 Torr can be achieved without compromising precursor stability. These results highlight N,N-disubstituted-N'-acylthiourea complexes as a versatile and tuneable platform for single-source precursor development.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"44 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021459","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}
Yahui Zhu, Senqun Liu, Wenbo Ye, Jiayao Chen, Shengjun Deng, Rong Zeng, Shunmin Ding, Chao Chen
As a key functional molecule in the organosilicon industry, the green synthesis of silyl ethers is crucial for materials science and pharmaceutical manufacturing. Addressing the dual bottlenecks of traditional alcoholysis processes (highly corrosive feedstocks/harmful byproducts) and existing catalysts (high precious metal costs, low non-precious metal efficiency), this study innovatively employs sulfur-containing porous organic polymers (POPs) combined with interfacial engineering strategies. Through precise control of pyrolysis and in-situ nickel salt impregnation, a nickel-sulfur species/heteroatom-doped porous carbon composite catalyst with abundant active interfaces was successfully constructed. Its high-performance catalytic mechanism stems from two key aspects: Interfacial electronic structure modulation: Heteratom-doped carbon supports optimize the d-band centers of nickel species through electronic induction effects. Interfacial defect dynamic construction: The NiS→Ni3S2 phase transition induces high-density sulfur vacancies (SVs) in the interfacial region, significantly enhancing substrate adsorption and activation capabilities. Leveraging the synergistic catalysis of this multifunctional interface, the silane- alcohol dehydrogenation coupling reaction achieves 99% conversion and 99% selectivity. This work establishes a novel “multifunctional interface synergistic catalysis” paradigm integrating electronic modulation, structural evolution, and defect engineering, providing theoretical support and practical solutions for economically sustainable organosilicon synthesis technologies.
{"title":"Dynamic Reconstructing Sulfur Vacancies-Rich Ni3S2 Interfaces for Highly Selective Silane-Alcohol Dehydrogenation Coupling","authors":"Yahui Zhu, Senqun Liu, Wenbo Ye, Jiayao Chen, Shengjun Deng, Rong Zeng, Shunmin Ding, Chao Chen","doi":"10.1039/d5dt02790j","DOIUrl":"https://doi.org/10.1039/d5dt02790j","url":null,"abstract":"As a key functional molecule in the organosilicon industry, the green synthesis of silyl ethers is crucial for materials science and pharmaceutical manufacturing. Addressing the dual bottlenecks of traditional alcoholysis processes (highly corrosive feedstocks/harmful byproducts) and existing catalysts (high precious metal costs, low non-precious metal efficiency), this study innovatively employs sulfur-containing porous organic polymers (POPs) combined with interfacial engineering strategies. Through precise control of pyrolysis and in-situ nickel salt impregnation, a nickel-sulfur species/heteroatom-doped porous carbon composite catalyst with abundant active interfaces was successfully constructed. Its high-performance catalytic mechanism stems from two key aspects: Interfacial electronic structure modulation: Heteratom-doped carbon supports optimize the d-band centers of nickel species through electronic induction effects. Interfacial defect dynamic construction: The NiS→Ni3S2 phase transition induces high-density sulfur vacancies (SVs) in the interfacial region, significantly enhancing substrate adsorption and activation capabilities. Leveraging the synergistic catalysis of this multifunctional interface, the silane- alcohol dehydrogenation coupling reaction achieves 99% conversion and 99% selectivity. This work establishes a novel “multifunctional interface synergistic catalysis” paradigm integrating electronic modulation, structural evolution, and defect engineering, providing theoretical support and practical solutions for economically sustainable organosilicon synthesis technologies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"52 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021962","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}
Payton A Fortuna,Leslie S G Kelley,Yipeng Sun,Jiabin Xu,Zhiqiang Wang,Paul D Boyle,Tsun-Kong Sham,Viktor N Staroverov,Johanna M Blacquiere
We report a phosphine 1-azaallyl ligand L2 [2-(diphenylphosphino)-2'-(3,3-dimethyl-1-azaallyl)-1,1'-biphenyl], which enables reversible coordination of Lewis bases through changes in ligand hapticity. In the palladium methyl complex [Pd(CH3)(L2)], L2 adopts a κ1-P;η3-NCC coordination mode. Pyridine binding induces reorganization to a κ2-PN mode, while reversion to the κ1-P;η3-NCC mode facilitates pyridine dissociation. These interconversions were established by 13C{1H} and 1H-31P HMBC NMR spectroscopy, X-ray absorption spectroscopy, and density-functional theory calculations. The results highlight a ligand-controlled mechanism for reversible substrate coordination based on tunable binding modes.
{"title":"A change in ligand hapticity promotes Lewis base dissociation.","authors":"Payton A Fortuna,Leslie S G Kelley,Yipeng Sun,Jiabin Xu,Zhiqiang Wang,Paul D Boyle,Tsun-Kong Sham,Viktor N Staroverov,Johanna M Blacquiere","doi":"10.1039/d5dt02402a","DOIUrl":"https://doi.org/10.1039/d5dt02402a","url":null,"abstract":"We report a phosphine 1-azaallyl ligand L2 [2-(diphenylphosphino)-2'-(3,3-dimethyl-1-azaallyl)-1,1'-biphenyl], which enables reversible coordination of Lewis bases through changes in ligand hapticity. In the palladium methyl complex [Pd(CH3)(L2)], L2 adopts a κ1-P;η3-NCC coordination mode. Pyridine binding induces reorganization to a κ2-PN mode, while reversion to the κ1-P;η3-NCC mode facilitates pyridine dissociation. These interconversions were established by 13C{1H} and 1H-31P HMBC NMR spectroscopy, X-ray absorption spectroscopy, and density-functional theory calculations. The results highlight a ligand-controlled mechanism for reversible substrate coordination based on tunable binding modes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"119 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146015169","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}
Muhammad Adnan Munir,Awais Khalid,Sana Ben Khalifa,Pervaiz Ahmad,Saleh Chebaane,Abdulaziz M Alanazi,Mudassir Hasan,Shahroz Saleem
In this study, a sol-gel auto-combustion technique was adopted to synthesize La3+-substituted CoFe2O4 (x = 0.00, 0.05, and 0.10) nanoparticles for use in electronic device applications by modifying the dielectric loss control of CFO nanoparticles. The PL spectra revealed a decrease in charge recombination at a doping content of x = 0.10 and an increase in charge recombination at a doping content of x = 0.20. The doping of x = 0.10 increases the particle size and crystallinity, which supports the decrease in dielectric loss by minimizing defect states, grain boundary density, and unwanted polarization mechanisms. When the doping concentration further increases to x = 0.20, the dielectric loss increases. A doping of x = 0.05 achieves the lowest tan δ (0.74), while x = 0.10 shows higher losses (1.5); the real part of the dielectric constant fluctuates between 48k and 170k and the imaginary part fluctuates between 118k and 313k. The higher ac conductivity of 0.126 was recorded for x = 0.05 La3+ doping composition at 1MHz, with significantly lower values of 0.017 for x = 0.00, and 0.013 μS cm-1 for x = 0.10. The obtained dielectric loss values suggest that the CFO nanoparticles with a lower lanthanum doping concentration (x = 0.10) presented in this study offer potential opportunities for use in electronic devices.
{"title":"Tailoring structural, photoluminescence, and dielectric properties of cobalt ferrite via La3+ doping for high-performance ceramic applications.","authors":"Muhammad Adnan Munir,Awais Khalid,Sana Ben Khalifa,Pervaiz Ahmad,Saleh Chebaane,Abdulaziz M Alanazi,Mudassir Hasan,Shahroz Saleem","doi":"10.1039/d5dt02104a","DOIUrl":"https://doi.org/10.1039/d5dt02104a","url":null,"abstract":"In this study, a sol-gel auto-combustion technique was adopted to synthesize La3+-substituted CoFe2O4 (x = 0.00, 0.05, and 0.10) nanoparticles for use in electronic device applications by modifying the dielectric loss control of CFO nanoparticles. The PL spectra revealed a decrease in charge recombination at a doping content of x = 0.10 and an increase in charge recombination at a doping content of x = 0.20. The doping of x = 0.10 increases the particle size and crystallinity, which supports the decrease in dielectric loss by minimizing defect states, grain boundary density, and unwanted polarization mechanisms. When the doping concentration further increases to x = 0.20, the dielectric loss increases. A doping of x = 0.05 achieves the lowest tan δ (0.74), while x = 0.10 shows higher losses (1.5); the real part of the dielectric constant fluctuates between 48k and 170k and the imaginary part fluctuates between 118k and 313k. The higher ac conductivity of 0.126 was recorded for x = 0.05 La3+ doping composition at 1MHz, with significantly lower values of 0.017 for x = 0.00, and 0.013 μS cm-1 for x = 0.10. The obtained dielectric loss values suggest that the CFO nanoparticles with a lower lanthanum doping concentration (x = 0.10) presented in this study offer potential opportunities for use in electronic devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146015167","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}
In this report, sustainable and environmentally benign approach was employed for the fabrication of niobium-doped zinc oxide nanoparticles (Nb/ZnO NPs) and their corresponding PVAc coated nanocomposites (PVAc-Nb/ZnO NCs). The synthesis was carried out under ambient conditions using Aegle marmelos L. leaf extract. Specifically, ZnO matrices doped with 5% and 10% Nb were successfully isolated, and subjected to a facile PVAc surface-coating procedure to enhance their physicochemical stability and catalytic performance. Isolated materials were comprehensively characterized using spectroscopic (UV–Vis, FT-IR), XRD, SEM, EDS, and BET analyses. XRD patterns confirmed the formation of single-phase crystalline ZnO without emergence of secondary impurity peaks, whereas FT-IR spectra verified presence of characteristic functional groups associated. SEM micrographs revealed distinct morphological features: a flower-petal for 5% Nb/ZnO and spherical agglomerates for 10% Nb/ZnO NPs. Notably, PVAc-coated samples exhibited increased agglomeration due to polymer encapsulation. The average particle size was found to be 19.7 nm and 16.3 nm for 5% and 10% Nb/ZnO NPs. While, in the case of PVAc-5% and 10% Nb/ZnO NCs, the average particle size was observed as 23.9 nm and 22.05 nm, respectively. BET analysis demonstrated significant enhancement in specific surface area following PVAc coating, increasing from 5 and 4 m² g⁻¹ (for 5% and 10% Nb/ZnO NPs, respectively) to 28 and 17 m² g⁻¹ for the corresponding PVAc-Nb/ZnO NCs. The photocatalytic efficiencies of all the synthesized materials were evaluated for the degradation of BPA and BTB under UV irradiation (9 W Hg lamp). The PVAc-Nb/ZnO NCs achieved remarkable degradation efficiencies, exceeding 92% for BPA and 90% for BTB within 50 minutes. Key operational parameters—including catalyst dosage, pollutant concentration, and irradiation time—were systematically optimized. The degradation kinetics for both pollutants followed a pseudo-first-order model. To elucidate the plausible degradation mechanism and identify intermediate species, radical-quenching experiments and LC–MS analyses were conducted. Importantly, recyclability studies demonstrated superior structural integrity and catalytic stability of the PVAc-coated samples across six to eight cycles for BPA and seven to nine cycles for BTB. In nutshell, the PVAc-Nb/ZnO NCs exhibit significantly enhanced photocatalytic performance, making them promising candidates for efficient removal of organic pollutants from contaminated water.
{"title":"Sustainable Fabrication of PVAc-Coated Nb–ZnO Nanocomposites by Aegle marmelos L. Extract for Enhanced Surface Activity towards Photocatalytic Degradation of Bisphenol A and Bromothymol Blue","authors":"Tanuj Tanuj, Anjali Anjali, Rajesh Kumar, Santosh Kumar, Dhiraj Singh Rawat","doi":"10.1039/d5dt02960k","DOIUrl":"https://doi.org/10.1039/d5dt02960k","url":null,"abstract":"In this report, sustainable and environmentally benign approach was employed for the fabrication of niobium-doped zinc oxide nanoparticles (Nb/ZnO NPs) and their corresponding PVAc coated nanocomposites (PVAc-Nb/ZnO NCs). The synthesis was carried out under ambient conditions using Aegle marmelos L. leaf extract. Specifically, ZnO matrices doped with 5% and 10% Nb were successfully isolated, and subjected to a facile PVAc surface-coating procedure to enhance their physicochemical stability and catalytic performance. Isolated materials were comprehensively characterized using spectroscopic (UV–Vis, FT-IR), XRD, SEM, EDS, and BET analyses. XRD patterns confirmed the formation of single-phase crystalline ZnO without emergence of secondary impurity peaks, whereas FT-IR spectra verified presence of characteristic functional groups associated. SEM micrographs revealed distinct morphological features: a flower-petal for 5% Nb/ZnO and spherical agglomerates for 10% Nb/ZnO NPs. Notably, PVAc-coated samples exhibited increased agglomeration due to polymer encapsulation. The average particle size was found to be 19.7 nm and 16.3 nm for 5% and 10% Nb/ZnO NPs. While, in the case of PVAc-5% and 10% Nb/ZnO NCs, the average particle size was observed as 23.9 nm and 22.05 nm, respectively. BET analysis demonstrated significant enhancement in specific surface area following PVAc coating, increasing from 5 and 4 m² g⁻¹ (for 5% and 10% Nb/ZnO NPs, respectively) to 28 and 17 m² g⁻¹ for the corresponding PVAc-Nb/ZnO NCs. The photocatalytic efficiencies of all the synthesized materials were evaluated for the degradation of BPA and BTB under UV irradiation (9 W Hg lamp). The PVAc-Nb/ZnO NCs achieved remarkable degradation efficiencies, exceeding 92% for BPA and 90% for BTB within 50 minutes. Key operational parameters—including catalyst dosage, pollutant concentration, and irradiation time—were systematically optimized. The degradation kinetics for both pollutants followed a pseudo-first-order model. To elucidate the plausible degradation mechanism and identify intermediate species, radical-quenching experiments and LC–MS analyses were conducted. Importantly, recyclability studies demonstrated superior structural integrity and catalytic stability of the PVAc-coated samples across six to eight cycles for BPA and seven to nine cycles for BTB. In nutshell, the PVAc-Nb/ZnO NCs exhibit significantly enhanced photocatalytic performance, making them promising candidates for efficient removal of organic pollutants from contaminated water.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021965","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}
Julian Buth, Yury V Vishnevskiy, Jan-Hendrik Lamm, Beate Neumann, Georg Stammler, Norbert Werner Mitzel
Sulphur-bridged frustrated Lewis pairs (FLPs) of the type Bis2E-S-PtBu2 (ESP; E = Al, Ga) were synthesised in analogy to their oxygen-bridged E-O-P analogues (EOP). An exchange reaction between AlSP and GaOP affords selectively and in accordance with the concept of hard and soft acids and bases (HSAB) the inverted systems AlOP and GaSP. Reactivity studies towards small molecules, such as CO2, CS2, SO2, N2O, and propylene sulphide, revealed differences in adduct formations. The adducts EXP·CX2 and EXP·SO2 (X = O, S) consist of five-membered heterocylces. The oxidation products EXP·X are four-membered rings; they result from the reaction of the EXP with N2O and/or propylene sulfide (under loss of propene), except the reaction of AlSP with propylene sulfide that forms a six-membered ring with the whole substrate molecule. The FLP GaSP is exceptional because the formation of its CO2 adduct is temperature-dependent, confirmed by variable-temperature NMR studies, and its adduct GaSP·CS2 has two structural isomers. All CS2 adducts impress with different colours in solution.
合成了Bis2E-S-PtBu2 （ESP; E = Al, Ga）型硫桥挫折刘易斯对（FLPs），与它们的氧桥E- o - p类似物（EOP）相似。AlSP和GaOP之间的交换反应选择性地根据软硬酸碱（HSAB）的概念提供了AlOP和GaSP的倒置体系。对小分子（如CO2、CS2、SO2、N2O和丙烯硫化物）的反应性研究揭示了加合物形成的差异。加合物EXP·CX2和EXP·SO2 （X = O， S）由五元杂环组成。氧化产物EXP·X为四元环；它们是由EXP与N2O和/或硫化丙烯（在失去丙烯的情况下）反应产生的，但AlSP与硫化丙烯的反应除外，后者与整个底物分子形成六元环。FLP GaSP是特殊的，因为它的二氧化碳加合物的形成与温度有关，经变温核磁共振研究证实，它的加合物GaSP·CS2有两个结构异构体。所有CS2加合物在溶液中都有不同的颜色。
{"title":"Tuning reactivity through implementation of the HSAB concept in oxygen- and sulphur-bridged Al/P and Ga/P FLPs","authors":"Julian Buth, Yury V Vishnevskiy, Jan-Hendrik Lamm, Beate Neumann, Georg Stammler, Norbert Werner Mitzel","doi":"10.1039/d6dt00151c","DOIUrl":"https://doi.org/10.1039/d6dt00151c","url":null,"abstract":"Sulphur-bridged frustrated Lewis pairs (FLPs) of the type Bis<small><sub>2</sub></small>E-S-P<em><small><sup>t</sup></small></em>Bu<small><sub>2</sub></small> (<strong>ESP</strong>; E = Al, Ga) were synthesised in analogy to their oxygen-bridged E-O-P analogues (<strong>EOP</strong>). An exchange reaction between <strong>AlSP</strong> and <strong>GaOP</strong> affords selectively and in accordance with the concept of <em>hard and soft acids and bases </em>(HSAB) the inverted systems <strong>AlOP</strong> and <strong>GaSP</strong>. Reactivity studies towards small molecules, such as CO<small><sub>2</sub></small>, CS<small><sub>2</sub></small>, SO<small><sub>2</sub></small>, N<small><sub>2</sub></small>O, and propylene sulphide, revealed differences in adduct formations. The adducts <strong>EXP</strong>·CX<small><sub>2</sub></small> and <strong>EXP</strong>·SO<small><sub>2</sub></small> (X = O, S) consist of five-membered heterocylces. The oxidation products <strong>EXP</strong>·X are four-membered rings; they result from the reaction of the <strong>EXP</strong> with N<small><sub>2</sub></small>O and/or propylene sulfide (under loss of propene), except the reaction of <strong>AlSP </strong>with propylene sulfide that forms a six-membered ring with the whole substrate molecule. The FLP <strong>GaSP</strong> is exceptional because the formation of its CO<small><sub>2</sub></small> adduct is temperature-dependent, confirmed by variable-temperature NMR studies, and its adduct <strong>GaSP</strong>·CS<small><sub>2</sub></small> has two structural isomers. All CS<small><sub>2</sub></small> adducts impress with different colours in solution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"71 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022160","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}
Vivien Wessels, Jasper A Baldauf, Rainer Pöttgen, Henning A. Höppe
So far, only a few sulfatomolybdates are known. Their anions feature mainly low dimensionalities. By choosing the respective reaction conditions, the new compounds β-K2[MoO2(SO4)2] and Na2[MoO2(SO4)2] can be synthesised, revealing layered structures, discovered for the first time for this material class. They comprise sulfate tetrahedra and molybdate octahedra connected via common edges, forming a vierer ring between the building units. While the potassium cations are fully ordered in β-K22[MoO2(SO4)2], the sodium cations exhibit disorder in Na2[MoO2(SO4)2] which does not vanish at higher temperatures. Additionally, the compound crystallises with an incommensurate modulated structure at room temperature which vanishes at higher temperatures. The titled compounds were characterised by single-crystal and powder XRD, MAPLE calculations, FT-IR, UV-vis spectroscopy, magnetic susceptibility and thermogravimetric analysis (TGA). The latter reveals fairly high thermal stabilities for both compounds.
{"title":"Stratified Sulfatometallates: Unlocking a New Dimension in Sulfatomolybdates","authors":"Vivien Wessels, Jasper A Baldauf, Rainer Pöttgen, Henning A. Höppe","doi":"10.1039/d5dt03061g","DOIUrl":"https://doi.org/10.1039/d5dt03061g","url":null,"abstract":"So far, only a few sulfatomolybdates are known. Their anions feature mainly low dimensionalities. By choosing the respective reaction conditions, the new compounds β-K<small><sub>2</sub></small>[MoO<small><sub>2</sub></small>(SO<small><sub>4</sub></small>)<small><sub>2</sub></small>] and Na<small><sub>2</sub></small>[MoO<small><sub>2</sub></small>(SO<small><sub>4</sub></small>)<small><sub>2</sub></small>] can be synthesised, revealing layered structures, discovered for the first time for this material class. They comprise sulfate tetrahedra and molybdate octahedra connected via common edges, forming a vierer ring between the building units. While the potassium cations are fully ordered in β-K2<small><sub>2</sub></small>[MoO<small><sub>2</sub></small>(SO<small><sub>4</sub></small>)<small><sub>2</sub></small>], the sodium cations exhibit disorder in Na<small><sub>2</sub></small>[MoO<small><sub>2</sub></small>(SO<small><sub>4</sub></small>)<small><sub>2</sub></small>] which does not vanish at higher temperatures. Additionally, the compound crystallises with an incommensurate modulated structure at room temperature which vanishes at higher temperatures. The titled compounds were characterised by single-crystal and powder XRD, MAPLE calculations, FT-IR, UV-vis spectroscopy, magnetic susceptibility and thermogravimetric analysis (TGA). The latter reveals fairly high thermal stabilities for both compounds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"143 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048694","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}
This study explores the applicability of magnetic zeolites from industrial waste-specifically fly ash (FA) combined with either synthetic Fe-based nanoparticles (FANPs1 and FANPs2) or red mud (RM) in differing ratios (FA1RM1 and FA4RM1)-for the removal and recovery of emerging water contaminants. FA and RM originate from coal combustion in thermoelectric power plants and alumina extraction from bauxite, respectively. The resulting materials were first assessed for acute toxicity on a freshwater model organism, revealing no acute effects. They were then tested under environmentally relevant conditions for the removal of ofloxacin (OFL), a fluoroquinolone antibiotic selected as a representative water-persistent contaminant. Subsequently, three extraction techniques-ultrasound-assisted extraction (UsAE), microwave-assisted extraction (MwAE), and magnetic hyperthermia-assisted extraction (MhAE)-were applied to recover the adsorbed OFL. All materials exhibited high OFL loading efficiencies (80-95%). Among the extraction techniques, MwAE yielded the highest OFL recovery (>80% for FANPs2 and FA4RM1), while UsAE and MhAE achieved lower efficiencies (up to ∼60%), regardless of the adsorbent used. Post-loading and post-extraction characterization studies provided insights into the adsorption mechanism and revealed significant OFL resorption across all zeolite types. Preliminary tests also confirmed the ability of these materials to capture endocrine-disrupting compounds (EDCs), underscoring their potential for water remediation and recovery applications.
{"title":"Upcycled materials for water treatment and emerging contaminant recovery: a preliminary study on waste-derived magnetic zeolites.","authors":"Claudia Belviso,Veronica Bonadeo,Maura Mancinelli,Maryam Abdolrahimi,Alessandro Lascialfari,Francesca Brero,Annalisa Martucci,Giacomo Diego Gatta,Marco Parolini,Davide Peddis,Antonio Lettino,Francesco Cavalcante,Lara Gigli,Federica Maraschi,Michela Sturini","doi":"10.1039/d5dt02472b","DOIUrl":"https://doi.org/10.1039/d5dt02472b","url":null,"abstract":"This study explores the applicability of magnetic zeolites from industrial waste-specifically fly ash (FA) combined with either synthetic Fe-based nanoparticles (FANPs1 and FANPs2) or red mud (RM) in differing ratios (FA1RM1 and FA4RM1)-for the removal and recovery of emerging water contaminants. FA and RM originate from coal combustion in thermoelectric power plants and alumina extraction from bauxite, respectively. The resulting materials were first assessed for acute toxicity on a freshwater model organism, revealing no acute effects. They were then tested under environmentally relevant conditions for the removal of ofloxacin (OFL), a fluoroquinolone antibiotic selected as a representative water-persistent contaminant. Subsequently, three extraction techniques-ultrasound-assisted extraction (UsAE), microwave-assisted extraction (MwAE), and magnetic hyperthermia-assisted extraction (MhAE)-were applied to recover the adsorbed OFL. All materials exhibited high OFL loading efficiencies (80-95%). Among the extraction techniques, MwAE yielded the highest OFL recovery (>80% for FANPs2 and FA4RM1), while UsAE and MhAE achieved lower efficiencies (up to ∼60%), regardless of the adsorbent used. Post-loading and post-extraction characterization studies provided insights into the adsorption mechanism and revealed significant OFL resorption across all zeolite types. Preliminary tests also confirmed the ability of these materials to capture endocrine-disrupting compounds (EDCs), underscoring their potential for water remediation and recovery applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"155 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146015153","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}
Tina Andrejević, Jovica Branković, Tatjana Ilic-Tomic, Nevena Stevanović, Bojana Pantović, Darko Ašanin, Jasmina Nikodinovic-Runic, Vladimir P Petrović, Violeta Marković, Biljana Glisic
N-methylphenothiazine (N-Mephtz) was used as a ligand for the synthesis of three new silver(I) complexes with the general formula [Ag(N-Mephtz)4]X·nH2O (X is CF3SO3- and n = 1/3 for 1, X is SbF6- and n = 0 for 2, and X is PF6- and n = 0 for 3). These complexes were characterized using spectroscopic methods, while their structures were determined by single crystal X-ray diffraction analysis. In all complexes, four N-Mephtz ligands are monodentately coordinated to the silver(I) ion through the sulfur atom, forming cationic [Ag(N-Mephtz)4]+ species, with CF3SO3–, SbF6– and PF6– acting as counterions for 1–3, respectively. Experimental IR band assignments were supported by DFT calculations, and TD-DFT simulations provided insight into their UV-Vis spectra. The antimicrobial activity of complexes 1–3 was evaluated against different bacterial and one fungal strain, with complex 1 exhibiting notable activity against all tested microorganisms, with MIC values ranging from 8 to 30 µg mL−1 (7.17 to 26.88 µM). Molecular docking screening identified eight potential antimicrobial protein targets among tested microorganisms. Cytotoxicity assessments revealed pronounced effects on human lung cancer (A549) and colon cancer (HCT116) cell lines, suggesting potential antiproliferative activity. However, the observed cytotoxicity toward mammalian cells also indicates the need for further structural refinement to improve selectivity for antimicrobial applications. The interactions of the complexes with calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) were examined to assess their biomolecular binding affinities. Binding constant (KA) indicated that complexes 1 and 3 have a similar binding affinity to this protein as N-Mephtz, while complex 2 demonstrated a lower affinity. All complexes exhibited significantly enhanced ct-DNA binding via the minor groove compared to the free ligand. Molecular docking confirmed strong minor groove DNA interactions and identified favorable BSA binding sites.
{"title":"Silver(I) complexes with N-methylphenothiazine as potential antimicrobial agents with a multi-target mode of action","authors":"Tina Andrejević, Jovica Branković, Tatjana Ilic-Tomic, Nevena Stevanović, Bojana Pantović, Darko Ašanin, Jasmina Nikodinovic-Runic, Vladimir P Petrović, Violeta Marković, Biljana Glisic","doi":"10.1039/d5dt02898a","DOIUrl":"https://doi.org/10.1039/d5dt02898a","url":null,"abstract":"N-methylphenothiazine (N-Mephtz) was used as a ligand for the synthesis of three new silver(I) complexes with the general formula [Ag(N-Mephtz)4]X·nH2O (X is CF3SO3- and n = 1/3 for 1, X is SbF6- and n = 0 for 2, and X is PF6- and n = 0 for 3). These complexes were characterized using spectroscopic methods, while their structures were determined by single crystal X-ray diffraction analysis. In all complexes, four N-Mephtz ligands are monodentately coordinated to the silver(I) ion through the sulfur atom, forming cationic [Ag(N-Mephtz)4]+ species, with CF3SO3–, SbF6– and PF6– acting as counterions for 1–3, respectively. Experimental IR band assignments were supported by DFT calculations, and TD-DFT simulations provided insight into their UV-Vis spectra. The antimicrobial activity of complexes 1–3 was evaluated against different bacterial and one fungal strain, with complex 1 exhibiting notable activity against all tested microorganisms, with MIC values ranging from 8 to 30 µg mL−1 (7.17 to 26.88 µM). Molecular docking screening identified eight potential antimicrobial protein targets among tested microorganisms. Cytotoxicity assessments revealed pronounced effects on human lung cancer (A549) and colon cancer (HCT116) cell lines, suggesting potential antiproliferative activity. However, the observed cytotoxicity toward mammalian cells also indicates the need for further structural refinement to improve selectivity for antimicrobial applications. The interactions of the complexes with calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) were examined to assess their biomolecular binding affinities. Binding constant (KA) indicated that complexes 1 and 3 have a similar binding affinity to this protein as N-Mephtz, while complex 2 demonstrated a lower affinity. All complexes exhibited significantly enhanced ct-DNA binding via the minor groove compared to the free ligand. Molecular docking confirmed strong minor groove DNA interactions and identified favorable BSA binding sites.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"39 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005679","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}
Alexandra A. Skatova, Andrey A. Bazanov, Evgeny V. Baranov, Mikhail A. Kiskin, Sergey Yu. Ketkov and Igor L. Fedushkin
Phosphaketenes are important versatile reagents in organophosphorus chemistry. We herein report on the synthesis of novel mono- and bis-phosphaketenes based on redox-active acenaphthene-1,2-diimine ligands (bian) and their reactions with bian-gallylene and a trityl radical. The interaction of diiodide gallium(III) [(ArBIG-bian)GaI2] (ArBIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with two equivalents of sodium phosphaethynolate [Na(PCO)(diox)0.5] gives the first paramagnetic phosphaketene [(ArBIG-bian)Ga(PCO)2] (1). Reaction of 1 with gallylene [(ArBIG-bian)Ga] leads to phosphaketene [(ArBIG-bian)Ga(PCO)] (2). Gallium phosphaketene [(ArBIG-bian)Ga(Py)(PCO)] (3) is formed as a result of the interaction between diimine ArBIG-bian and excess gallium metal in the presence of gallium chloride in pyridine and a subsequent metathesis reaction with sodium phosphaethynolate. The addition of a trityl radical to 3 produces a sterically hindered alkyl complex [(ArBIG-bian)Ga(CPh3)] (4). New compounds 1–4 have been characterized by ESR (1) and NMR (2–4) spectroscopy; their molecular structures have been established by single-crystal X-ray analysis. The electronic structures of 1–4 and reaction thermodynamics were studied by DFT calculations.
{"title":"Gallium phosphaketenes derived from bis(imino)acenaphthenes (bian): synthesis and reactivity towards a trityl radical and bian-gallylene","authors":"Alexandra A. Skatova, Andrey A. Bazanov, Evgeny V. Baranov, Mikhail A. Kiskin, Sergey Yu. Ketkov and Igor L. Fedushkin","doi":"10.1039/D5DT02466H","DOIUrl":"10.1039/D5DT02466H","url":null,"abstract":"<p >Phosphaketenes are important versatile reagents in organophosphorus chemistry. We herein report on the synthesis of novel mono- and bis-phosphaketenes based on redox-active acenaphthene-1,2-diimine ligands (bian) and their reactions with bian-gallylene and a trityl radical. The interaction of diiodide gallium(<small>III</small>) [(Ar<small><sup>BIG</sup></small>-bian)GaI<small><sub>2</sub></small>] (Ar<small><sup>BIG</sup></small>-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with two equivalents of sodium phosphaethynolate [Na(PCO)(diox)<small><sub>0.5</sub></small>] gives the first paramagnetic phosphaketene [(Ar<small><sup>BIG</sup></small>-bian)Ga(PCO)<small><sub>2</sub></small>] (<strong>1</strong>). Reaction of <strong>1</strong> with gallylene [(Ar<small><sup>BIG</sup></small>-bian)Ga] leads to phosphaketene [(Ar<small><sup>BIG</sup></small>-bian)Ga(PCO)] (<strong>2</strong>). Gallium phosphaketene [(Ar<small><sup>BIG</sup></small>-bian)Ga(Py)(PCO)] (<strong>3</strong>) is formed as a result of the interaction between diimine Ar<small><sup>BIG</sup></small>-bian and excess gallium metal in the presence of gallium chloride in pyridine and a subsequent metathesis reaction with sodium phosphaethynolate. The addition of a trityl radical to <strong>3</strong> produces a sterically hindered alkyl complex [(Ar<small><sup>BIG</sup></small>-bian)Ga(CPh<small><sub>3</sub></small>)] (<strong>4</strong>). New compounds <strong>1–4</strong> have been characterized by ESR (<strong>1</strong>) and NMR (<strong>2–4</strong>) spectroscopy; their molecular structures have been established by single-crystal X-ray analysis. The electronic structures of <strong>1–4</strong> and reaction thermodynamics were studied by DFT calculations.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 5","pages":" 2080-2087"},"PeriodicalIF":3.3,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005066","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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