Dalton Transactions最新文献

{"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)>SiC-MnO(II)>SiC-Mn2O3(III)>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}

{"title":"Metal Complexes with a Twist: Modified Rhodamines as a Promising Theranostic Approach for Combating Cancer","authors":"Fábio Martins, Maria da Graça P. M. S. Neves, Ana M.G. Silva","doi":"10.1039/d4dt03575e","DOIUrl":"https://doi.org/10.1039/d4dt03575e","url":null,"abstract":"Rhodamines have been recognized for their exceptional optical properties, making them suitable for detection, imaging, and disease diagnosis. However, their use as photosensitizers in Photodynamic Therapy (PDT) has been limited by their low singlet oxygen production and limited tissue penetration. The development of rhodamine-metal complexes has overcome these limitations, offering a promising new approach for cancer treatment. These complexes in combination with structural and optical tuning of rhodamines, have been engineered to enhance tumour cell selectivity, improve reactive oxygen species (ROS) generation, and mitochondrial-targeted delivery. Notably, a variety of metal ions, including iridium(III), ruthenium(II) and platinum(II/IV) can form complexes with bright rhodamines with excellent optical responses and remarkable ROS generation. These breakthroughs have the potential to improve cancer diagnosis and therapeutic applications. Photophysical properties, photostability, and targeting agents, particularly in the near-infrared (NIR) range, will be discussed, with a focus on their applications in cancer detection, localization, and cytotoxicity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"72 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862303","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":"Non-piezoelctric SiO2 amorphous nanomaterials for highly tribocatalytic water purification","authors":"Yan Zhang, Junling Che, Yuhang Gao, Cuijin Pei, Yanmin Jia","doi":"10.1039/d5dt00732a","DOIUrl":"https://doi.org/10.1039/d5dt00732a","url":null,"abstract":"Being widely available in the rock layers of the earth, SiO2 is among the earth's most thoroughly distributed natural mineral resources. Here, the non-piezoelectric amorphous SiO2 mineral nanoparticles have been experimentally designed for the efficiently tribocatalytic dye degradation under mechanical friction provided by the 400~1200 rpm low-velocity stirring. The friction between the catalysts’ surface and the stirring rod leads to the generation of these positive and negative charges to respectively react with the hydroxide and oxygen in the dye solution to produce some active substances, yielding to tribocatalytic organic dye degradation. After being mechanically stirred at 1000 rpm for 6 h using amorphous SiO2 mineral nanoparticle catalysts, ~95.2% Rhodamine B dye can be obviously degraded. These radical trapping experiments show that ·OH and ·O2- are the main active substances. Furthermore, increasing the contact area or the friction contact interface's roughness is helpful for enhancing the tribocatalytic performance. After 3 recycling cycles, the SiO2 nanoparticles can still degrade ~89.2% RhB dye. The low-cost SiO2 mineral nanoparticles, with these advantages of being widely distributed, are potential to harvest environmental common mechanical friction energy for the application of organic pollution degradation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862304","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":"Rationally Tailored Passivator with Multisite Surface-anchors for Suppressing Ion Migration toward Air-Stable Perovskite Solar Cells","authors":"Yiqing Chen, Dandan Luo, Dingyu Xia, Fei Wang, Chong Jia, Qiang Zhao, Xinhua Li","doi":"10.1039/d5dt00352k","DOIUrl":"https://doi.org/10.1039/d5dt00352k","url":null,"abstract":"Trap states in perovskite films fabricated from solution-method can capture photo-generated carriers, expedite ion migration, and contribute to decomposition of perovskite layer, thereby emerging as a major threat to the commercialization of perovskite solar cells (PSCs). To address these issues, passivation of surface traps on perovskite films via molecules with functional groups has been proved to be one of the most effective tactics for obtaining high-performance PSCs. Herein, potassium nonafluoro-1-butanesulfonate (KNFBS) molecules with multiple chemical bonds including multisite F atoms, sulfonic acid group and K ions were introduced as surface-anchoring passivators to improve the film quality as well as passivate trap states. Based on the in situ conductive atomic force microscopy (C-AFM) and Kelvin probe force microscopy (KPFM) results, it was found that undercoordinated Pb and I vacancy defects on the surface and grain boundaries (GBs) of perovskite films can be synergistically curtailed via multiple chemical interaction including Lewis acid-base, hydrogen and ionic bonds, respectively. Moreover, the influence of the varied ligands on defect and the halide ion migration in perovskites as well as the mechanism behind it have been extensively explored. Therefore, the KNFBS-treated perovskite films with a more homogeneous surface potential distribution, significantly reduced point, vacancy defect and dangling bond density, and facilitated charge transfer, resulted in an optimized power conversion efficiency (PCE) of 20.88% and enhanced air stability for the PSCs fabricated and stored in fully open-air condition. The work has not only elucidated the fundamental mechanisms of ion migration and multisite passivation at surface and GBs of perovskites, but also probes into the ligand design strategies for further improving the performance of perovskite photovoltaics.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"13 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862256","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":"MgO nanoparticles decorated in-situ nitrogen doping porous carbon hybrid materials as advanced sulfur host in Li-S batteries","authors":"Linyue Qu, Dongyuan Lei, Yang Bai, Ming Wu Xiang, Wei Bai, Jun-Ming Guo, Xinzhou Yang, Zixian Yang","doi":"10.1039/d5dt00475f","DOIUrl":"https://doi.org/10.1039/d5dt00475f","url":null,"abstract":"Porous carbon combined with metal oxides modification shows great potential applications in lithium sulfur batteries due to these merits including high encapsulation capacity for active sulfur, short transport path for lithium ions and good trapping capability of lithium polysulfides. Herein, inspired by waste biomass passion fruit peels, an in-situ nitrogen doping porous carbon hybrid material with MgO nanoparticles decoration is designed and constructed via hydrothermal treatment and synchronous activation/carbonization method. The as-prepared porous carbon exhibits abundant pore structure with notably large specific surface area of 2221.8 m<small>²</small>·g<small>^-1</small>, mainly consisting of meso- and micro-pores. Even with the MgO nanoparticles modification, a high specific surface area of 1063.2 m<small>²</small>·g<small>^-1</small> is still retained for sulfur loading and electrolyte penetration. Especially the combination of rich pores, moderate MgO nanoparticles and nitrogen doping exhibits good physicochemical synergistic effect for well alleviating the shuttle dissolution of polysulfides. When the carbon hybrid material is evaluated as sulfur host, the optimized battery delivers an initial discharge capacity of 792.5 mAh·g<small>^-1</small> at 0.2 C and a high reversible capacity of 668 mAh g<small>^-1</small> after 200 cycles. Besides, a stable long cycle performance upto 1000 cycles is also achieved at a high current rate of 1.0 C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858171","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}