Dalton Transactions最新文献

{"title":"Luminescence quenching of pyrene-labeled fluorescent dendrons by surface anchoring of ruthenium nanoparticles","authors":"Roberto González Gómez, Mireille Vonlanthen, Christian Bijani, Catherine Amiens, Ernesto Rivera, Karine Philippot","doi":"10.1039/d5dt00192g","DOIUrl":"https://doi.org/10.1039/d5dt00192g","url":null,"abstract":"Hybrid nanostructures comprising ruthenium nanoparticles (Ru NPs) and Fréchet type dendrons of first (G1) and second (G2) generations bearing two and four pyrene units, respectively, and a carboxylic acid group as an anchoring function, have been prepared by taking advantage of the organometallic approach and ligand exchange. Their optical properties have been studied by absorption and fluorescence spectroscopies and compared with those of counterparts prepared in the same conditions but with pyreneacetic acid and pyrenebutyric acid as fluorophores. Pyrene-labelled Fréchet type dendrons display more pyrene units at a longer distance from the Ru surface than pyreneacetic acid and pyrenebutyric acid fluorophores. Interestingly, and unlike pyreneacetic acid- and pyrenebutyric acid-derived nanohybrids, the dendron-functionalized Ru NPs exhibit significant to efficient quenching of the pyrene fluorescence (67% for G2 and 94% for G1 with respect to the free dendrons). The quenching effect of the Ru metallic cores onto the fluorophore units opens up new prospects for the use of such nanohybrids as antennas for photocatalytic applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"87 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797936","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":"Ferrocene conjugated Os(ii) complex for photo-catalytic cancer therapy of triple-negative breast cancer cells†","authors":"Apurba Mandal, Virendra Singh, Silda Peters, Arif Ali Mandal, Tumpa Sadhukhan, Biplob Koch and Samya Banerjee","doi":"10.1039/D5DT00515A","DOIUrl":"10.1039/D5DT00515A","url":null,"abstract":"<p >A novel ferrocene-conjugated bimetallic Os(<small>II</small>) photocatalyst (<strong>OsFe</strong>) showed micromolar photocatalytic anticancer activity against triple-negative breast cancer cells <em>via</em> NADH oxidation and caspase 3 activation under visible light.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 17","pages":" 6785-6789"},"PeriodicalIF":3.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789987","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":"Facile preparation of carbon, nitrogen co-doped NiMoO4·MoO2 heterostructures derived from polyoxometalate with ultrahigh energy density for zinc-ion capacitors","authors":"Yining Zhang, Yangyang Wen, Xiaoying Liu, Yingnan Zhang, Xiaoxue Jia, Wang Li, Hongxuan Tang, Hongfei Dou, Yannan Li, Yan Zhao","doi":"10.1039/d5dt00505a","DOIUrl":"https://doi.org/10.1039/d5dt00505a","url":null,"abstract":"Aqueous zinc ion hybrid supercapacitors (ZHSC) have attracted great attention in recent years. However, their electrochemical performance is prohibited by the low energy density and poor cycling stability, mainly due to the difficulty in effectively activating the ionic and electronic conductivity of the cathode material. In this work, we innovatively propose a low-cost, precisely customized strategy for doping trace amounts of carbon and nitrogen elements into metal oxides to improve electrochemical performance. The carbon and nitrogen-doped NiMoO4·MoO2/NC heterostructures derived from polyoxometalates maintain high electrochemical activity while achieving high ionic conductivity. Trace amounts of carbon and nitrogen elements can significantly improve electronic conductivity and charge storage capacity. Due to the synergistic contribution, the composite structure with multi-redox sites exhibits a high specific capacity value of 364.96 F/g at 1 A/g in 1 M ZnSO4. A ZHSC was assembled with NiMoO4·MoO2/NC as the cathode and zinc sheet as the anode. After 10000 cycles, the capacitance retention rate still reached over 80 %. In addition, its energy density and power density can also reach 102 Wh Kg-1@4140 W Kg-1, which is higher than that of MoO2-based traditional supercapacitors. This strategy fully demonstrates the great practicality and development prospects of polyoxometalate derivatives for ZHSC.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789985","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-zeolites synthesis from Amazonian kaolinite for methylene blue removal: adsorption and photocatalytic activity","authors":"Victor Augusto Araújo de Freitas, Débora Souza Pinheiro, Camila Ferreira Peixoto, Luiz Oliveira, Paulo Rogério da Costa Couceiro","doi":"10.1039/d5dt00439j","DOIUrl":"https://doi.org/10.1039/d5dt00439j","url":null,"abstract":"Zeolites exhibit high adsorption capacities for organic substrates and catalytic activity owing to their unique structural features, such as uniform pore sizes and Lewis acidity. However, their inherent UV-Vis transparency (λ &gt; 240 nm) limits their efficacy as photocatalysts. This limitation can be addressed by incorporating transition metals into their framework or encapsulating semiconductors within their porous structures. In this study, Fe-zeolites were synthesized through alkaline fusion of natural Amazonian kaolinite, followed by hydrothermal treatment with varying Fe³⁺ loadings from Fe(NO₃)₃. In the absence of Fe(NO₃)₃, LTA zeolite was obtained under these experimental conditions. However, the introduction of Fe(NO₃)₃ led to the formation of cancrinite (CAN) zeolite, suggesting that nitrate anions acted as a structure-directing agent. XRD and Mössbauer spectroscopy confirmed the presence of Fe-doped cancrinite and dispersed maghemite within FeZEO-3 and FeZEO-5. Methylene blue adsorption onto Fe-zeolites was best described by the Langmuir isotherm model and followed pseudo-second-order kinetics. An increase in iron content from 0 to 5% (w/w) led to enhanced photoactivity, as evidenced by a decrease in band gap energy from 3.21 eV to 2.93 eV and finally to 2.53 eV. This improved photoactivity was further supported by the observation of hydroxylated methylene blue intermediates during the photocatalysis process as the material FeZEO-5 removed up to 90% of the dye.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"313 1-2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789983","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":"Unusual zig-zag-shape Ln-radical coordination networks derived from a nitronyl nitroxide with two imidazole groups: single-crystal to single-crystal transformations and magnetic properties","authors":"Chaoyi Jin, Qiuxue Zhang, Jinkui Tang, Peng Cheng, Licun Li","doi":"10.1039/d4dt03488k","DOIUrl":"https://doi.org/10.1039/d4dt03488k","url":null,"abstract":"Two unusual two-dimensional coordination networks, namely, {[Gd(hfac)<small>₃</small>]<small>₃</small>(NITPh-3,5-bIm)<small>₂</small>}‧2.25C<small>₆</small>H<small>₁₄</small> (1) and {[Dy(hfac)<small>₃</small>]<small>₃</small>(NITPh-3,5-bIm)<small>₂</small>}‧2.5 C<small>₆</small>H<small>₁₄</small> (2), have been achieved utilizing the multidentate nitronyl nitroxide ligand containing two additional imidazole groups NIT-Ph-3,5-bIm (NIT-Ph-3,5-bIm = 2-[3,5-bis(1-imidazole)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroacetylacetonate). In these Ln-radical complexes, the multidentate nitronyl nitroxide radical ligand serves as a tridentate linker to bind three LnIII ions via one NO group and two imidazole units of the radical, resulting in unique zig-zag-shape 2D networks with KIa topology. These coordination networks can undergo a single-crystal to single-crystal transformation from low-temperature non-centrosymmetric space group (<em>P</em>2<small>₁</small>) to room temperature centrosymmetric space group (<em>P</em>2<small>₁</small>/c) accompanied by the helicity loss of chiral chains and an order−disorder transition of Ln<small>^III</small> ions. Direct-current magnetic susceptibility studies of the Gd derivative shows dominant ferromagnetic Gd-NO exchange. Dynamic magnetic studies of Dy analogs display temperature-dependent nonzero out of out-of-phase signals indicating slow magnetic relaxation behavior.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"72 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789986","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":"Exploring Catalytic Activity Modulations: Photoredox Catalysis with Substituted Copper(I)-Dipyridylamine Derivatives","authors":"Alondra Villegas-Menares, Yannik Hansmann, Max Bayas, Camilo Verdugo, Ignacio Erazo, César Zúñiga-Loyola, Ivan Gonzalez, Antonio Galdámez, Lucrezia Villa, Mirco Natali, Alan Raul Cabrera","doi":"10.1039/d4dt03337j","DOIUrl":"https://doi.org/10.1039/d4dt03337j","url":null,"abstract":"In this work we have successfully synthesized five new heteroleptic copper(I) complexes (<strong>C1–5</strong>), bearing <em>N,N</em> ligands derived from dipyridylamine and <em>S</em>-BINAP as the <em>P,P</em> auxiliary ligand. All complexes were structurally characterized using NMR, FT-IR, and elemental analysis. Furthermore, the molecular structures of <strong>C1</strong>, <strong>C4</strong>, and <strong>C5</strong> were determined via X-ray diffraction analysis. The photophysical properties of all complexes were assessed using UV-Vis spectroscopy and spectrofluorometric measurements in dichloromethane solution the solid state. All complexes displayed absorption bands at lower energies, attributed to spin-allowed MLCT transitions. In degassed dichloromethane solution at room temperature, all complexes exhibited broad luminescence in the visible spectrum, mainly assigned to MLCT/LLCT phosphorescence, with excited state lifetimes in the μs time regime. Besides, all complexes were assessed as photoredox catalysts in chlorosulfonylation and bromonitromethylation reactions of styrene, showing remarkable performances, thus highlighting the privileged role of the dpa ligand for the design of Earth-abundant metal photocatalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789984","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":"In situ synthesis of a Bi2O3/Bi2S3 composite heterojunction for the electrochemical characterization of supercapacitors†","authors":"Wenting Chen, Jiacheng Zheng, Yulong Deng, Chengliao Deng, Xiaoming Cai, Jinming Cai and Honglin Tan","doi":"10.1039/D5DT00026B","DOIUrl":"10.1039/D5DT00026B","url":null,"abstract":"<p >This study employs a two-step hydrothermal method to <em>in situ</em> introduce sulfur into a Bi<small>₂</small>O<small>₃</small> matrix. The synthesized material displays a specific capacitance of 305.57 F g<small>⁻¹</small> (2 A g<small>⁻¹</small>) and achieves a cycling stability of 94.12% (10 A g<small>⁻¹</small>), evidencing the enhancement of both capacitance and cycling stability attributed to the heterojunction. The existence of a built-in electric field was confirmed <em>via</em> theoretical calculations, highlighting the interactions between the electrode materials and ions. In addition, devices were constructed to demonstrate the practicality in real-world applications. This study proposes an effective methodology for the <em>in situ</em> synthesis of heterojunctions, offering fresh perspectives on the development of electrode materials for supercapacitors.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 17","pages":" 7029-7038"},"PeriodicalIF":3.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776132","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":"Hollow CoNiFe ternary metal selenide electrocatalysts derived from Prussian blue analogues for boosting the oxygen evolution reaction†","authors":"Mingyang Cai, Weishun Song, Ziling Huang, Xiaoquan Yang, Junjie Fu, Lin Luo, Xueming Su, Hongwei Gu and Xueqin Cao","doi":"10.1039/D5DT00447K","DOIUrl":"10.1039/D5DT00447K","url":null,"abstract":"<p >The development of effective electrocatalysts is a top priority for the oxygen evolution reaction (OER), which is the crucial half-reaction of water electrolysis, since electrocatalytic water splitting for hydrogen production offers a practical solution to the upcoming energy crisis. Herein, we report a strategy to fabricate hollow ternary metal selenide (CoNiFe–Se) nanocubes derived from Prussian blue analogues (PBAs) by phytic acid etching and low-temperature gas-phase selenization. Due to the advantages of its multi-component composition and hollow structure, CoNiFe–Se exhibited a low overpotential of 275 mV@10 mA cm<small>⁻²</small>, a small Tafel slope of 62.3 mV dec<small>⁻¹</small> and a long-term stability of more than 80 h in 1.0 M KOH. This research offers an innovative idea and a straightforward technique for preparing hollow multimetallic selenide electrocatalysts derived from PBAs.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 17","pages":" 7039-7048"},"PeriodicalIF":3.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776130","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":"Pb–Pd alloy catalysts with intercalated Pb atoms: optimized electronic and lattice structures for enhanced electrochemical ethanol oxidation†","authors":"Yonghui Ye, Yu Zhang, Xintong Yan, Gong Ning and Shi Hu","doi":"10.1039/D5DT00117J","DOIUrl":"10.1039/D5DT00117J","url":null,"abstract":"<p >A facile one-step method is employed to synthesize carbon-supported Pd–Pb binary metal catalysts for the ethanol oxidation reaction (EOR) in alkaline electrolytes. A variety of characterization techniques have demonstrated that the alloying of Pd with Pb alters the electronic structure and induces lattice expansion. Electrochemical tests for the EOR in alkaline electrolytes demonstrated that the Pd<small>₃</small>Pb/C catalyst exhibited the highest mass activity (3.59 A mg<small>_Pd</small><small>⁻¹</small>) and specific activity (17.97 mA cm<small>⁻²</small>), which are 4.6 and 4.7 times those of the Pd/C catalyst prepared by the same method, respectively. The intercalation of lead atoms has altered both the lattice and the electronic structure of palladium, leading to opposing shifts in the d-band center that collectively optimize the adsorption strength of CO* and OH*, key intermediates of the EOR. Consequently, the Pd<small>₃</small>Pb/C electrocatalyst exhibits significant EOR catalytic activity. This study provides a viable implementation plan and analytical strategy for optimizing palladium-based catalysts with non-noble metals by integrating electronic transfer, bifunctional effects, and d-band center adjustments for bimetallic catalysts.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 17","pages":" 7071-7079"},"PeriodicalIF":3.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776134","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":"Palladium(II) and Platinum(II) Complexes of Disubstituted Imidazo[1,5-a]Pyridine and Imidazolylpyridine: Coordination Chemistry, Versatile Catalysis, Biophysical Study","authors":"AMLAN RANJAN RAYASINGH, Vadivelu Manivannan","doi":"10.1039/d5dt00346f","DOIUrl":"https://doi.org/10.1039/d5dt00346f","url":null,"abstract":"Some pincer type mono- and poly-nuclear Pd(II) and Pt(II) complexes bearing imidazo[1,5-a]pyridine and imidazolylpyridine moiety were synthesized and characterized by using several spectroscopic methods. Determination of molecular structures of all complexes by single crystal X-ray diffraction studies revealed a distorted square planar geometry around the bivalent palladium and platinum in all complexes. These Pd(II) complexes have been observed to display high catalytic activity in various reaction such as Suzuki-Miyaura cross-coupling reaction, transfer hydrogenation reaction, and alkyne homocoupling. The theoretical study was also well matched with experimental data of all catalysts. Substantial deviations in the catalytic activity were observed by changing the co-ligand, binding mode of the ligand and the number of metal centre. Under optimal conditions, Suzuki cross-coupling and the transfer hydrogenation reaction were accomplished proficiently with wide functional group possibility by taking only 0.1 mol% of tetranuclear Pd(II) complex (5) as catalyst. Intermediates in Suzuki coupling reaction were also detected by using mass spectroscopy. Among all studied complexes, the tetra nuclear palladium complex exhibited high catalytic activity. Further Pd(II) complexes were tested in a model reaction of homocoupling of phenylacetylene and produce diphenylbutadiyne in excellent yield. Also, interaction study of all the complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were investigated using electronic spectroscopy Absorption study showed minor groove binding of DNA with these complexes while intercalative binding was observed by all complexes through displacement of ethidium bromide (EB) in EB-DNA by quenching of fluorescence intensity. The complexes were also displayed high binding affinity toward BSA confirmed by emission, synchronous fluorescence, and steady state fluorescence anisotropy measurement. Moreover, the pharmacokinetic properties of two bioactive compounds (3s and 3t) obtained from Suzuki coupling reaction were calculated and to evaluate their activity as leukotriene A4 hydrolase (LTA4H) inhibitor, these molecules were docked with human LTA4H enzyme.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776133","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}