Dalton Transactions最新文献_第10页

Rapid synthesis of fault-free GME zeolite

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00508f

Jingqiu Li, Caiping Sheng, Ye Ma, Liangni Ban, Jie Zhu, Zhongping Huang, Hongxia Shen, Xuebo Cao, Longfeng Zhu

{"title":"Rapid synthesis of fault-free GME zeolite","authors":"Jingqiu Li, Caiping Sheng, Ye Ma, Liangni Ban, Jie Zhu, Zhongping Huang, Hongxia Shen, Xuebo Cao, Longfeng Zhu","doi":"10.1039/d5dt00508f","DOIUrl":"https://doi.org/10.1039/d5dt00508f","url":null,"abstract":"Optimization of the synthesis of known zeolite structures and discovery of their new applications are continuously the hot topics in the field of zeolite chemistry. One of the typical examples is GME zeolite structure. Herein, we for the first time report a rapid synthesis of fault-free GME zeolite by the combined strategy of seeding and aging. The fault-free GME zeolite could be obtained at 160 °C for only 2.5 h. Various characterization techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM) and nuclear magnetic resonance (NMR) have been used, which shows that the obtained product has good crystallinity, perfect hexagonal morphology, fully 4-coordinated Al species plus its fault-free feature. In addition, after the post-treatment of as-made GME zeolite, Na-GME zeolite with large BET surface area and high porosity could be obtained successfully. More importantly, the obtained Na-GME zeolite is firstly used for CO2 capture, giving the high CO2 adsorption of 5.37 mmol/g and excellently selective CO2 adsorption from CO2/N2 (15/85, v/v) with separation coefficient of 58.8. The fault-free GME zeolite used for CO2 capture might be potentially of significance for its industrial application.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640191","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

In-situ Formed Ag Nanoparticle Decorated LiMn2O4 Cathodes with Outstanding Electrochemical Performance

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00511f

Wangqiong Xu, Qiling Li, Shubiao Xia, Zhe Li, Feixiang Cheng, Shimei Guo

引用次数: 0

Chromium Catalyzed Acceptorless Dehydrogenative (Cross)Coupling of Primary Amines to Secondary Imines

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d4dt03460k

Aman Anand, Anitta Regina, Sachin Jalwal, Soumojyati Prodhan, Debangsu Sil, Manikandan Paranjothy, Subrata Chakraborty

引用次数: 0

A Revised Understanding of the Speciation of Gold(III) Dithiocarbamate Complexes in Solution

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00240k

Ryan Brown, Joseph N. Bunyan, Ashi Agrawal, Guoyu Li, Dominykas Dautoras, Jagodish C Sarker, Terng Tor Keat, Thomas Hicks, Graeme Hogarth, David Pugh

{"title":"A Revised Understanding of the Speciation of Gold(III) Dithiocarbamate Complexes in Solution","authors":"Ryan Brown, Joseph N. Bunyan, Ashi Agrawal, Guoyu Li, Dominykas Dautoras, Jagodish C Sarker, Terng Tor Keat, Thomas Hicks, Graeme Hogarth, David Pugh","doi":"10.1039/d5dt00240k","DOIUrl":"https://doi.org/10.1039/d5dt00240k","url":null,"abstract":"The cytotoxic series of cis-platin mimics “[AuX2(dtc)]” (X = Cl, Br; dtc = dithiocarbamate) were recently patented as promising anticancer metallotherapeutics. Using a range of dialkyl-, cyclic alkyl- and diaryl-dithiocarbamate ligands, we have discovered that “[AuX2(dtc)]” actually exist in solution as a mixture containing neutral [AuX2(dtc)] and cationic [Au(dtc)2]+. For the latter, single crystal X-ray crystallography proved that a variety of halide-containing anions such as [AuX4]–, [AuX2]– and even X– balanced the charge. Based on a thorough investigation into the synthesis of these compounds, we discovered that literature syntheses which claim to produce pure material in fact generate mixtures. In some cases the major component of the mixture is actually the cationic [Au(dtc)2]+ rather than the claimed neutral [AuX2(dtc)]. Refinement of the synthetic conditions led to a mixture where the neutral [AuX2(dtc)] was the dominant component, from which pure solid [AuX2(dtc)] could be obtained by fractional crystallisation. However, the isomerisation process immediately restarted upon dissolution of the crystalline material, thus it is not possible to obtain pure [AuX2(dtc)] in solution. This discovery has important ramifications for any future use of these compounds, especially as therapeutics since the solution-phase speciation means that “pure” [AuX2(dtc)] cannot exist under biologically relevant conditions. A critical reinterpretation of existing literature data demonstrates that there is already significant uncertainty surrounding which component(s) of this mixture are biologically active.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640084","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 crucial role of acetonitrile in the mechanism of Pd(II)-catalyzed activation of polar vinyl monomers.†

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00340g

Chiara Alberoni, Barbara Milani, Esaie Reusser, Gabriele Balducci, Enzo Alessio, Martin Albrecht

{"title":"The crucial role of acetonitrile in the mechanism of Pd(II)-catalyzed activation of polar vinyl monomers.†","authors":"Chiara Alberoni, Barbara Milani, Esaie Reusser, Gabriele Balducci, Enzo Alessio, Martin Albrecht","doi":"10.1039/d5dt00340g","DOIUrl":"https://doi.org/10.1039/d5dt00340g","url":null,"abstract":"The migratory insertion reaction of a polar vinyl monomer into the Pd–alkyl bond and the chain walking process are two of the key steps in the catalytic cycle for the synthesis of functionalized polyolefins through coordination/insertion polymerization. Here we present a detailed NMR investigation to gain insight into these fundamental steps and demonstrate the critical role of traces of MeCN in this process. We used Pd(II) complexes containing a N–N' bidentate pyridyl-pyridylidene amide (py-PYA) ligand, which are known to cooligomerize ethylene and methyl acrylate (MA). The reaction of three related Pd–(py-PYA) complexes, viz. neutral [Pd(CH3)Cl(py-PYA)], 1a, and cationic derivatives [Pd(CH3)(NCCH3)(py-PYA)][X], X = BArF 1b, PF6 1c, with either MA or N,N-dimethylacrylamide (DMA), showed distinct reactivity with the two polar monomers. While 4-, 5-, and 6-membered palladacycles, resulting from the migratory insertion reaction of the polar monomer into the Pd–CH3 bond and subsequent chain walking, were detected with both monomers, their amounts varied considerably with the type of polar monomer, the anion, and the amount of MeCN. Specifically, we found that the coordinating ability of MeCN plays a critical and ambivalent role: on one hand, it hampers the coordination and insertion of the polar olefin, and on the other hand it markedly suppresses the chain walking process. Moreover, we report here the first solid state structure of a 5-membered metallacyclic species derived from DMA insertion into the Pd–CH3 bond. The palladacylic complexes are remarkably robust towards ethylene, though they react with carbon monoxide to form the palladium acyl species opening perspectives for these complexes to catalyze CO/DMA copolymerization.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"69 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640089","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

A mixed isocyanide Mn(I) complex and its reduction to a metallate

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00634a

Guilhem Claude, Mathias Ellwanger, Ritchie Hernandez, Adam Grippo, Joshua S. Figueroa, Ulrich Abram

引用次数: 0

Fabrication of a hierarchical PtIr@Rh hollow trimetallic nanozyme with a higher specific activity than HRP for sensitive colorimetric detection

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-18 DOI: 10.1039/d5dt00083a

Kai Cai, Jincheng Yuan, Jian Hao, Zeyang Yu, Shengyang Hu, Chenghui Zhai, Jiawei Liu

{"title":"Fabrication of a hierarchical PtIr@Rh hollow trimetallic nanozyme with a higher specific activity than HRP for sensitive colorimetric detection","authors":"Kai Cai, Jincheng Yuan, Jian Hao, Zeyang Yu, Shengyang Hu, Chenghui Zhai, Jiawei Liu","doi":"10.1039/d5dt00083a","DOIUrl":"https://doi.org/10.1039/d5dt00083a","url":null,"abstract":"Nanozymes have emerged as promising alternatives to natural enzymes in various fields, owing to their advantages in stability, cost-effectiveness, and multifunctionality. However, their relatively low catalytic activity compared to natural enzymes remains a major challenge for practical applications. Here, we developed a hierarchical PtIr@Rh hollow trimetallic nanorods, where Rh served as the substrate and the surface was decorated with numerous Pt nanoparticles doped with a small amount of Ir. The resulting nanorods exhibited remarkable peroxidase-like activity, with a specific activity of 2287 U mg-1, surpassing that of horseradish peroxidase (HRP). Additionally, the maximum reaction velocity (Vmax) was 1.024× 10-6 M s-1, and the Michaelis−Menten constant (Km) was 1.706 mM. The enhanced catalytic performance was attributed to the unique hierarchical structure and the small amount of Ir doping, as supported by density functional theory (DFT) calculations. The PtIr@Rh nanozyme was successfully applied for the colorimetric detection of L-ascorbic acid, achieving a rapid detection with a limit of detection (LOD) of 0.12 µM. This study introduces a novel nanozyme with superior specific activity compared to natural enzyme, highlighting its potential for colorimetric sensing applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654240","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

Modulating the Catalytic Properties of Decavanadate Hybrids Using a Mixed Counterion Strategy for Selective Oxidation of Thiophene-based Sulfides and Detoxification of Mustard Gas Simulant

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-17 DOI: 10.1039/d5dt00102a

Chullikkattil P. Pradeep, Kousik Routh, Aranya Kar

{"title":"Modulating the Catalytic Properties of Decavanadate Hybrids Using a Mixed Counterion Strategy for Selective Oxidation of Thiophene-based Sulfides and Detoxification of Mustard Gas Simulant","authors":"Chullikkattil P. Pradeep, Kousik Routh, Aranya Kar","doi":"10.1039/d5dt00102a","DOIUrl":"https://doi.org/10.1039/d5dt00102a","url":null,"abstract":"Selective oxidation of sulfides to sulfoxides, especially thiophene-based sulfides, is a challenging task. Herein, we report a mixed counterion strategy to tune the selectivity of sulfoxidation reaction catalyzed by decavanadate cluster-based hybrids using H2O2 as the oxidant under ambient conditions. By employing two different aryl sulfonium counterions (ASCIs) bearing different organic functional groups (phenol/aldehyde/salicylaldehyde/2,6-diformyl phenol) in a 1:1 synthetic feed ratio, we have generated a series of decavanadate cluster-based hybrids HY1-HY6. Different functional groups on the periphery of hybrids HY1-HY6 helped control the efficiency and selectivity of the sulfoxidation reaction by fine-tuning the electronic and supramolecular effects of these hybrids as catalysts. Further, these hybrids were also applied as catalysts for detoxifying 2-chloroethyl ethyl sulfide (CEES), a mustard gas simulant. The hybrid HY5, with a structural formula (DFHPDS)2(FPDS)2[H2V10O28](H2O)3(DFHPDS = (3,5-diformyl-4-hydroxyphenyl)dimethylsulfonium, and FPDS = (4-formylphenyl)dimethylsulfonium) showed the best catalytic properties in the series, with up to 99 % conversion and 85 % and 99 % selectivity towards sulfoxide in the case of dibenzothiophene (DBT) and CEES, respectively. This study's findings open new avenues for tuning the catalytic properties of POM-based hybrids toward selective organic transformation reactions by using a mixed counterion strategy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"42 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635308","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

Modulation of the spin crossover behaviour in four manganese(III) complexes through cation-anion interactions

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-17 DOI: 10.1039/d5dt00238a

Suvamoy Malik, Paula Brandão, Samia Benmansour Souilamas, Carlos J. Gomez Garcia, Amrita Saha

{"title":"Modulation of the spin crossover behaviour in four manganese(III) complexes through cation-anion interactions","authors":"Suvamoy Malik, Paula Brandão, Samia Benmansour Souilamas, Carlos J. Gomez Garcia, Amrita Saha","doi":"10.1039/d5dt00238a","DOIUrl":"https://doi.org/10.1039/d5dt00238a","url":null,"abstract":"Here we report the synthesis, structural and magnetic characterization of a series of manganese(III) monomers, formulated as [Mn(L)]X with X = PF6¯ (1), BF4¯ (2), I¯ (3) and Br¯/NO3¯ (4). These four compounds have been prepared with a Schiff base ligand (H2L) formed by 1:2 condensation of eugenol scaffold aldehyde and N,N′-bis(3-aminopropyl)ethylene-diamine. The structure of compounds 1-4 shows in all cases the presence of the same [MnIII(L)]+ cation surrounded by different X ¯ anions. Interestingly, the anions play a key role in determining not only the symmetry and cation-anion packing, which are quite different in compound 1 compared to compounds 2-4, but also the magnetic properties of the [MnIII(L)]+ cation. Variable temperature magnetic measurements show that in compound 1 the MnIII centre is in the high spin S = 2 state at any temperature, whereas compounds 2-4 show a smooth and incomplete spin crossover (SCO) from the low spin (S = 1) to the high spin (S = 2) ground state in the temperature range 200-400 K. At 400 K the high spin fractions are around 31 %, 27 % and 42 % for compounds 2-4, respectively. Isothermal magnetization measurements at low temperatures confirm the spin ground states in all cases. The magnetic data can be very well reproduced with a simple monomeric S = 2 (in 1) or S = 1 (in 2 4, for the low spin state) model with a zero field splitting (ZFS) contribution (and a very weak intermolecular antiferromagnetic interaction in 2 and 4). Additionally, a detailed analysis of the structural parameters in compounds 2-4 shows that the Mn-N bond distances, the continuous Shape parameters, the trigonal distortion angles (Φ) and the octahedral distortion parameters (Σ) show a significant increase when the temperature is increased from 100 to 398 K, confirming the presence of an incomplete SCO between 100 and 398 K in compounds 2-4.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635177","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

Enhancements of the first and second hyperpolarizability of a GMP coordination polymer: crystal structure and computational studies†

IF 3.5 3区化学

Dalton Transactions Pub Date : 2025-03-17 DOI: 10.1039/D5DT00248F

Mubashar Ilyas, Maroof Ahmad Khan, Lin Xiong, Li Zhang, Muhammad Lauqman, Muhammad Abbas, Hafiz Muhammad Zohaib, Nagesh Manurkar and Hui Li

{"title":"Enhancements of the first and second hyperpolarizability of a GMP coordination polymer: crystal structure and computational studies†","authors":"Mubashar Ilyas, Maroof Ahmad Khan, Lin Xiong, Li Zhang, Muhammad Lauqman, Muhammad Abbas, Hafiz Muhammad Zohaib, Nagesh Manurkar and Hui Li","doi":"10.1039/D5DT00248F","DOIUrl":"10.1039/D5DT00248F","url":null,"abstract":"A chiral cobalt coordination complex {[Co(GMP)(BPE)(H2O)3]·9H2O}n (1) has been studied and characterized by X-ray single crystal and powder diffraction. The crystal structural study of complex 1 reveals a 1D coordination polymer with a space group of P1 and a triclinic crystal system, which are packed in a crystal lattice via H-bonding and π–π interactions. The crystal packing's stabilization and intermolecular interactions of the complex are explored by crystallography combined with Hirshfeld surface analysis. The model complex 1 exhibits stupendous enhanced second harmonic generation (SHG), with intensity up to 2.1 times that of potassium dihydrogen phosphate (KDP). Computational studies (DFT and TD-DFT) explain the emergence of the first and second hyperpolarizability in complex 1, in which the first hyperpolarizability is associated with non-centrosymmetry and hydrogen bonding and the remarkably enhanced second hyperpolarizability originates from intramolecular charge transfer. The computed βSHG of complex 1 is 27.70 and 3.79 times higher than those of KDP and para-nitroaniline (p-NA), respectively. The simultaneous presence of first and second hyperpolarizability suggests that the synthesized complex 1 could be a promising candidate for nonlinear optical materials with potential applications in optoelectronic devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 14","pages":" 5921-5934"},"PeriodicalIF":3.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635310","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