Dalton Transactions最新文献

{"title":"The effect of substituents on the P-P and P=C bond properties in phosphanylphosphaalkenes","authors":"Aleksandra Ziolkowska, Wiktoria Błaszkiewicz, Tomasz Kruczyński","doi":"10.1039/d5dt00692a","DOIUrl":"https://doi.org/10.1039/d5dt00692a","url":null,"abstract":"A new lithium salt of diphosphane, (<em>i</em>Pr₂N)PhP-P(SiMe₃)Li (<strong>2</strong>), featuring two electronically differentiated substituents, is presented. Its reaction with benzophenone was then carried out, yielding a novel phosphanylphosphaalkene (3). The isolated compound was subsequently treated with <em>n</em>BuLi and PhLi to obtain stable activators (<strong>3a</strong> and <strong>3b</strong>) for the potential polymerization of phosphorus-rich compounds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872380","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}

{"title":"Theoretical Study on the Modulation of Oxygen Electrocatalysis in Co-Based Single-Atom Catalysts by N and S Co-Coordination","authors":"Rui He, Xinyu Zhang, Linlin Zhang, Nan Chen, Zhen Gao, Yanning Wang, Kai Xiong","doi":"10.1039/d5dt00771b","DOIUrl":"https://doi.org/10.1039/d5dt00771b","url":null,"abstract":"Understanding how local coordination environments influence oxygen electrocatalytic activity is essential for designing efficient non-precious metal catalysts. In this work, density functional theory (DFT) calculations were performed to systematically explore the impact of N/S co-coordination on the electronic structure and catalytic properties of graphene-supported cobalt single-atom catalysts (SACs). The results demonstrate that all Co–N–S configurations exhibit negative formation energies and positive dissolution potentials, suggesting favorable thermodynamic and electrochemical stability. Among these configurations, CoN₂S₂-pen shows a lower oxygen reduction reaction (ORR) overpotential of 0.53 V, while CoN₂S₂-hex exhibits superior oxygen evolution reaction (OER) performance with an overpotential of 0.42 V. Analyses of charge density differences and projected density of states (PDOS) reveal strong hybridization between Co 3d and O 2p orbitals, which facilitates O₂ activation and stabilizes intermediate adsorption. These findings underscore the potential of N/S co-coordination in modulating the electronic structure and enhancing the bifunctional oxygen electrocatalytic performance of Co-based SACs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"24 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872413","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}

{"title":"Nanosensors for hazardous pesticides and nanofertilizers for sustainable agricultural: Contribution of carbon quantum dots","authors":"Tumpa Biswas, Jiko Raut, Diptiman De, Prithidipa Sahoo","doi":"10.1039/d5dt00633c","DOIUrl":"https://doi.org/10.1039/d5dt00633c","url":null,"abstract":"The increasing global population threatens food security, necessitating sustainable agricultural practices. Intensive farming has led to the excessive use of pesticides and fertilizers, contaminating soil and water sources causing the impairment of the environment. Pesticide residues enter the food chain, posing serious health risks like neurotoxicity, genetic mutations, and diseases such as Alzheimer's, Parkinson's, diabetes, etc. Conventional detection methods are costly, complex, time- consuming, unsuitable for onsite detection, and mostly are not eco-friendly. Fluorescent-based nano-biosensors, particularly carbon quantum dots (CQDs), offer a promising alternative to detect pesticides and herbicides due to their high sensitivity, biocompatibility, low toxicity, and photostability. In addition to its sensory application, CQDs could be used as an alternative to conventional chemical fertilizers for crop production. CQDs-based nano fertilizers improve nutrient absorption, boost plant growth, and increase resistance to environmental stressors. This review will highlight the key advancements of CQDs in terms of various synthetic techniques and their usage as nanosensors and nano fertilizers.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"13 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872382","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}

{"title":"(C5N2H7)IO2F2 and (C3N6H8)(IO2F2)2 : Two new organic-inorganic hybrid fluoroiodate birefringent crystals","authors":"Si Yuan, Chun-Li Hu, Jiang-Gao Mao","doi":"10.1039/d5dt00524h","DOIUrl":"https://doi.org/10.1039/d5dt00524h","url":null,"abstract":"Birefringent crystals are anisotropic material commonly used in modern optical devices to obtain polarized light. Traditional commercial birefringence crystals, such as, MgF<small>₂</small> and CaCO<small>₃</small>, have the problems of small birefringence and not easy to grow. Herein, two organic-inorganic hybrid birefringence crystals composed of π-conjugated organic groups and lone pair-containing (IO<small>₂</small>F<small>₂</small>)<small>^-</small> anions, namely, (C<small>₅</small>N<small>₂</small>H<small>₇</small>)IO<small>₂</small>F<small>₂</small> and (C<small>₃</small>N<small>₆</small>H<small>₈</small>)(IO<small>₂</small>F<small>₂</small>)<small>₂</small>, were successfully grown by a simple evaporation method. In their structures, the π-conjugated organic cations and (IO<small>₂</small>F<small>₂</small>)<small>^-</small> anions are interconnected through hydrogen bonding and π-π stacking interactions into 3D supramolecular networks. Both of them exhibit large birefringence of 0.30 @ 550 nm and 0.23 @ 550 nm, superior to most of conventional birefringence materials. Moreover, UV-Vis-NIR diffuse reflectance spectra demonstrate that they have wide band gaps (4.06 eV and 4.10 eV) because of the presence of the F element with strong electronegativity. Theoretical analyses suggest that the parallel arrangement of the π conjugated cations resulted in large optical anisotropy. This work provides new promising candidates for UV birefringence materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872416","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}

{"title":"Selective detection of SO2 in NU-1000 via organometallic nickel silylphosphine post-synthetic complex incorporation","authors":"Juan L. Obeso, Luz Barrios-Vargas, Valeria López-Cervantes, Yoarhy Amador-Sánchez, Nancy Martín-Guaregua, Ricardo A. Peralta, Ramon Munoz, Ana Martínez, Carolina Leyva, Diego Solis-Ibarra, Elí Sánchez-González, Ilich A. Ibarra, Virginia Montiel-Palma","doi":"10.1039/d3dt03985d","DOIUrl":"https://doi.org/10.1039/d3dt03985d","url":null,"abstract":"The adsorption and detection of SO2 using Zr-based MOF, NU-1000 grafted with an organometallic nickel silylphosphine complex ([NiSi]@NU-1000) via post-synthetic modification are reported. [NiSi]@NU-1000 exhibits high stability under dry and wet SO2, with a high cyclability performance. Moreover, fluorescence experiments postulate [NiSi]@NU-1000 as a promising SO2 detector due to its high SO2 selectivity over CO2 and air, showing an evident quenching effect, especially at low SO2 concentrations (0.1 bar of SO2). Time-resolved photoluminescence experiments suggest that host-guest SO2 interactions are associated with the turn-off effect.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866466","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}

{"title":"Interplay of Cu···Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper(I) halide complexes with the derivatives of 4-pyrazolylpyrimidine-2-thiol","authors":"Sofia Skvortsova, Fyodor Verkhov, Elena B Nikolaenkova, Marianna I Rakhmanova, T. E. Kokina, Taisiya Sergeevna Sukhikh, Nikita Shekhovtsov, Mark B Bushuev","doi":"10.1039/d5dt00498e","DOIUrl":"https://doi.org/10.1039/d5dt00498e","url":null,"abstract":"Bicyclic pyrazolylpyrimidine compounds, 2-benzylthio-4-(3,5-dimethyl-1H-pyrazol-1-yl)pyrimidine (LH) and 2-benzylthio-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6-methylpyrimidine (LMe) were synthesized and studied as ligands for the preparation of copper(I) halido complexes. In the solid state, LH and LMe demonstrate dual excitation-wavelength dependent emission, i.e. fluorescence at higher excitation energies and phosphorescence at lower excitation energies due to the presence of a heavy sulphur atom. The reactions of LH and LMe with CuBr and CuI afforded a series of centrosymmetric binuclear complexes of the [Cu2L2Hal2] type (L = LH, Hal = Br, I; L = LMe, Hal = I). The possibility of rotation of the benzylthio group relative to the pyrazolylpyrimidine core leads to the isolation of two polymorphic modifications of the copper(I) iodido complex with LH, which differ by the Cu···Cu distance by more than 0.2 Å (2.86 Å for [Cu2(LH)2I2] (form I) vs. 2.65 Å for [Cu2(LH)2I2] (form II)). The isolation of the [Cu2(LH)2I2] complex in two different crystalline forms made it possible to reveal the influence of a rarely explored factor, namely the change in the Cu···Cu distance in a single molecule, on the photoluminescence quantum efficiency. Two structural indices, τdim, which showcases the degree of merging of CuLHal monomers into the centrosymmetric [Cu2L2Hal2] dimers, and τplan, which characterises the degree of planarization of the N2CuHal2CuN2 unit, were introduced and used for combined experimental and theoretical analysis of the relation between the structure of the complexes and their luminescence. All complexes exhibit phosphorescence of the ligand-to-halide charge transfer (LXCT) character in the orange region. According to TDDFT calculations, an increase in the Cu···Cu distance facilitates structural rearrangement in the T1 state followed by a rapid decrease in the T1-S0 energy gap and subsequent non-radiative decay via electron-phonon coupling, which substantiates the higher photoluminescence quantum yield (PLQY) of [Cu2(LH)2I2] (form II) (Cu···Cu 2.65 Å) compared to [Cu2(LH)2I2] (form I) (Cu···Cu 2.86 Å).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"73 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872414","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}

{"title":"The Role of Manganese Oxidation State in SF6 Degradation Performance of SiC-Supported Composites","authors":"Yaru Zhang, Xiang Meng, boxu Dong, Fengxiang Ma, Zhao Yue, Xinhua He, Shan Zhu, Jiantao Zai","doi":"10.1039/d5dt00714c","DOIUrl":"https://doi.org/10.1039/d5dt00714c","url":null,"abstract":"Sulfur hexafluoride (SF6) is a potent greenhouse gas with a significant impact on the environment and there is a need to develop effective degradation strategies. In this study, a series of composites with Mn-based metal active centers were synthesized using a simple and efficient milling method with SiC as the carrier to determine the effect of different valence states of Mn on SF6 degradation. The results showed that the degradation performance of SF6 by Mn-based composites with different valence states had an obvious hierarchy: SiC-Mn(0)&gt;SiC-MnO(II)&gt;SiC-Mn2O3(III)&gt;SiC-MnO₂(IV). Among them, the SiC-Mn composites with Mn monomers as active centers reach 62.27 mL/g at 600 °C. This performance trend is attributed to the stronger electron supplying ability of the lower valence Mn species, which enhances the cleavage of the strong S-F bonds in SF6. This study emphasizes the importance of the valence states of Mn in determining the catalytic efficiency of Mn-based composites for SF6 degradation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866468","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}

{"title":"CsCl−Flux Synthesis of Titanium Oxynitride Ti2.85O4N for Photocatalysis","authors":"Xiaoxuan Xie, Zihan Wang, Yatong Wang, Wenqian Chen","doi":"10.1039/d5dt00406c","DOIUrl":"https://doi.org/10.1039/d5dt00406c","url":null,"abstract":"The molten salt method is a key approach for preparing high−performance metal oxide photocatalysts, though its use in metal oxynitrides remains limited. In this work, we successfully synthesized titanium oxynitride Ti2.85O4N using CsCl flux method and evaluated the photocatalytic properties. The impact of CsCl addition at different synthesis stages was systematically studied. The addition of CsCl significantly enhanced the crystallinity of the oxynitrides, reducing defects and improving the overall material quality. Specifically, Ti2.85O4N−Cl−Cl, which incorporated CsCl during both precursor synthesis and oxynitride synthesis, exhibited the highest visible−light photocatalytic activity. In photocatalytic tests, Ti2.85O4N−Cl−Cl demonstrated a remarkable degradation rate of 77% for methylene blue under visible light irradiation within 120 minutes, which is approximately 1.97 times higher than that of the Cs0.68Ti1.83O4 precursor. The reaction rate constant for Ti2.85O4N−Cl−Cl was determined to be 0.00899 min−1, indicating efficient electron-hole separation and utilization of visible light. Our findings open a new direction for high−performance oxynitride synthesis, highlighting the potential of the molten salt method in enhancing the photocatalytic properties of metal oxynitrides.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866469","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}

{"title":"Fe and Cu co-doping induces abundant oxygen vacancies in MnO2 for efficient ozone catalytic oxidation of toluene at room temperature","authors":"Xinuo Cai, Jiahong Liao, Yushui Jiang, Yani Zhang, Lixia Qiu, Lecheng Lei, Xingwang Zhang, Chunlin Yu","doi":"10.1039/d5dt00289c","DOIUrl":"https://doi.org/10.1039/d5dt00289c","url":null,"abstract":"MnO<small>₂</small> holds significant potential for room-temperature ozone catalytic oxidation of volatile organic compounds (VOCs), yet it encounters challenges related to low degradation efficiency. This study introduces a co-doping strategy aimed at enhancing the catalytic activity and stability of MnO<small>₂</small>. Specifically, Mn<small>⁴⁺</small> ions were substituted with low-valence copper and iron dopants <em>via</em> a straightforward one-step hydrothermal method, resulting in the formation of abundant oxygen vacancies on the catalyst surface through driven redox precipitation. The resultant Fe–Cu–MnO<small>₂</small> catalyst exhibited remarkable catalytic performance at room temperature, achieving 100% toluene degradation and 100% ozone removal efficiency, along with an impressive mineralization ratio of 81.2% and sustained stability over 100 hours. Relevant experiments demonstrated that the improvement in catalytic activity was primarily attributed to the significant increase in oxygen vacancy concentration induced by co-doping. This was accompanied by increased surface oxygen adsorption and enhanced low-temperature reducibility, which facilitated the generation of reactive oxygen species. Additionally, co-doping induced crystal morphology changes and specific surface area expansion contribute to exposing more active sites, thereby enhancing catalytic performance. Consequently, the catalyst exhibited superior ozone catalytic oxidation performance for toluene degradation. <em>In situ</em> DRIFTS analysis further elucidated the degradation pathway and reaction mechanism of ozone catalytic oxidation of toluene. These findings may provide valuable insights for the development of efficient catalysts for low-temperature catalytic ozonation of VOCs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"31 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866467","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}

{"title":"The connection between Hydride Affinity and Local Electrophilicity: A key factor in designing frustrated Lewis pairs for reversible H2 activation","authors":"César Barrales-Martínez, Rocío Durán, Julio Caballero, Pablo Jaque","doi":"10.1039/d4dt03455d","DOIUrl":"https://doi.org/10.1039/d4dt03455d","url":null,"abstract":"We present a clear relationship between hydride affinity and the condensed-to-boron electrophilicity index for 27 intramolecular aminoborane frustrated Lewis pairs (FLPs), employing Density Functional Theory calculations. First, the Gibbs free energy change's dependence of H<small>₂</small> splitting on the hydride affinity of the FLPs is explored, identifying strong linear correlations for aromatic and aliphatic nitrogen substituents. Additionally, we found that the condensed-to-boron electrophilicity index's inverse and logarithm show strong linear relationships with hydride affinity across all FLP systems, generating a direct connection between a purely theoretical reactivity index with an experimental property like the hydride affinity. Using these models, we applied our findings to an experimentally tested FLP system, predicting hydride affinity values that yield ∆G for H<small>₂</small> splitting of -0.2 and 0.9 kcal/mol with the inverse and logarithmic relationships, respectively, closely matching the experimental value of -1.7 ± 4.0 kcal/mol. These results confirm the predictive power of our models, which can be used to guide the rational design of new aminoborane FLPs to be employed in reversible H<small>₂</small> activation and metal-free hydrogenation of unsaturated compounds.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862255","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}