Dalton Transactions最新文献

{"title":"Electrical conductivity of low-doped ceria-based ceramics","authors":"Igor Zagaynov, Sergey V. Fedorov, Olga Antonova","doi":"10.1039/d4dt03165b","DOIUrl":"https://doi.org/10.1039/d4dt03165b","url":null,"abstract":"Ceria-based ceramic materials (M0.01Ce0.99O2) were successfully synthesized by the co-precipitation method and sintered at 1000 °C for 4 h in air. The electrical conductivity of these systems was measured by AC impedance spectroscopy at 500-750 °C in air; it has been established that the small introduction of dopants such as copper, bismuth, samarium, and neodymium increased this parameter by 4-5 times. However, the optimal dopants are Bi or Nd due to their higher conductivity and oxide ion transference number.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154099","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":"ortho-Nb2O5 as a recyclable heterogeneous catalyst for the synthesis of 2-substituted benzimidazoles and quinazolinones in an aqueous medium via oxidative dehydrogenative coupling","authors":"Rajasekharan Jayakumari Deepak, Thiagu Pavin, Ramasamy Karvembu","doi":"10.1039/d5dt00353a","DOIUrl":"https://doi.org/10.1039/d5dt00353a","url":null,"abstract":"Niobium pentoxide with deformed orthorhombic phase (ortho-Nb2O5) is found to be an efficient heterogeneous catalyst for the synthesis of N-heterocyclic compounds such as 2-substituted benzimidazoles and quinazolinones from primary alcohols via oxidative dehydrogenative coupling in an aqueous medium. The highlights of this environmentally benign method involve using bench-stable, heterogeneous, and biologically inert niobium metal-based catalyst, and the catalytic system is free of toxic metals, additives, oxidants, solvents, and byproducts. The catalyst is compatible with different substrates, and the desired benzimidazoles and quinazolinones were obtained with moderate to good yields. The catalyst is recyclable and used five times without much loss in activity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165639","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":"Chemistry of Silylated Rare Earths and Heavier f-Elements: Ready to Enter the Next Stage","authors":"Christoph Marschner","doi":"10.1039/d5dt00956a","DOIUrl":"https://doi.org/10.1039/d5dt00956a","url":null,"abstract":"The last few years have witnessed exciting development in the chemistry of silylated rare earths and heavier f-elements. First examples of silylated lanthanum (La) and praseodymium (Pr) complexes have been reported so that currently out of all lanthanides only for the radioactive promethium (Pm) silylated complexes are unknown. Previously unknown U(III) silyl complexes have also been described. Spectacular examples of the elusive trisilylated complexes of lanthanides and actinides have been presented. These show unusual magnetic properties, making them susceptible to facile 29Si NMR spectroscopic characterization, which could be rather difficult for compounds with diminished silylation degree. Novel silylene complexes were shown to to catalyze hydrosilylation reactions. The novel compound class of silole coordinated f-element complexes was introduced by La and erbium (Er) complexes with the latter exhibiting single molecule magnetic properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154101","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":"Synthesis and characterisation of uniform CoPt nanoparticles using red blood cell ghosts conjugated with peptides on their inner surface","authors":"Shota Matsumoto, Zhang Yiyang, Nobuto Yoshinari, Kazuma Yasuhara, Masaaki Ohba, Tomomi Koshiyama","doi":"10.1039/d5dt00502g","DOIUrl":"https://doi.org/10.1039/d5dt00502g","url":null,"abstract":"Hybrids of metal nanoparticles (NPs) and lipid vesicles are attractive materials in a wide variety of fields including catalysis, sensing, and biomedical applications. Lipid vesicles can entrap metal NPs on their surfaces, in the lipid bilayer, or within their aqueous cores, resulting in the stabilisation of metal NPs in aqueous environments. Metal NP-lipid vesicle hybrids have been prepared using lipid film hydration in the presence of colloidal metal NPs and in situ synthesis of metal NPs within lipid vesicles. Although these methods are useful for preparing metal NP-lipid vesicle hybrids, they generally suffer from low yield, poor selectivity, and low purity. Moreover, it is still difficult to precisely control the formation process of metal NPs, and the nanospace of lipid vesicles is too small to deposit a large number of metal NPs. We described here the design of a red blood cell ghosts (RBCGs), micro-sized biological membranes, for the synthesis of bimetallic cobalt-platinum nanoparticles (CoPt NPs) with diverse functions such as excellent magnetic properties and catalytic activities. RBCGs are red blood cells from which cytoplasmic components are removed by hypotonic haemolysis. Notable structural features of RBCG include biconcave hollow vesicles with large volume and surface area and the presence of a cytoskeleton composed of proteins beneath the inner membrane. The cytoskeleton allows the immobilisation of various functional molecules on the internal surface by the chemical modification. To deposit uniform CoPt NPs on the inner surface of RBCG, we fabricated RBCG in which a CoPt-binding peptide was chemically attached to the RBCG cytoskeleton. In situ synthesis of CoPt NPs was performed using peptide-conjugated RBCGs or RBCGs under the various conditions. Metal quantification, TEM and magnetic measurement reveal that CoPt NPs prepared using peptide-conjugated RBCGs have larger and uniform NPs with higher Co content than those prepared using RBCGs, resulting in improved magnetic properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"69 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154102","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":"Synthesis of bulky hydride ligands: m-terphenylborohydride complexes with trivalent uranium and neodymium","authors":"Peter A. Zacher, Daniel K. Unruh, Scott R. Daly","doi":"10.1039/d5dt01076d","DOIUrl":"https://doi.org/10.1039/d5dt01076d","url":null,"abstract":"Here we describe the first coordination complexes containing a bulky <em>m</em>-terphenyltrihydroborate ligand. Treating [UI<small>₃</small>(thf)<small>₄</small>] and NdCl<small>₃</small> with three equiv. of Li(H<small>₃</small>BAr<small>^{<em>t</em>Bu4}</small>)(Et<small>₂</small>O) (where Ar<small>^{<em>t</em>Bu4}</small> = 2,6-(3,5-<small>^<em>t</em></small>Bu<small>₂</small>C<small>₆</small>H<small>₃</small>)<small>₂</small>C<small>₆</small>H<small>₃</small>) yielded [M(H<small>₃</small>BAr<small>^{<em>t</em>Bu4}</small>)<small>₃</small>(thf)<small>₂</small>] (M = U and Nd). [U(H<small>₃</small>BAr<small>^{<em>t</em>Bu4}</small>)<small>₃</small>(dme)<small>₂</small>] is also described, and structural comparisons reveal the influence of the Lewis base on H<small>₃</small>BAr<small>^{<em>t</em>Bu4}</small> positioning.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"153 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154100","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":"Operando Raman and ex situ characterization of an iron-based conductive MOF as a negative electrode in Li-ion batteries","authors":"Isabel Ciria-Ramos, Alex R. Neale, Laurence Hardwick, Emilio J. Juarez-Perez, Ignacio Gascón, Marta Haro","doi":"10.1039/d5dt00893j","DOIUrl":"https://doi.org/10.1039/d5dt00893j","url":null,"abstract":"An iron-based electrically conductive Metal-Organic Framework (MOF), Fe-HHTP, formed by the coordination of Fe cations and the organic ligand HHTP (2,3,6,7,10,11-hexahydroxytriphenylene), has been synthesized, characterized, and explored as a potential negative electrode for lithium-ion batteries (LIBs). Galvanostatic cycling experiments, with a lower cut-off voltage of 0.1 V vs. Li/Li+, reveal that Fe-HHTP undergoes a significant activation process, resulting in an increase in specific capacity up to 1142 mAh g-1 after ⁓220 cycles at a current of 355 mA g-1. Operando Raman spectroscopy during the first lithiation, complemented by ex situ techniques at different cycling stages, demonstrates that both the organic ligands and metal centers actively contribute to Li⁺ storage. Initially, lithiation occurs primarily at the MOF boundaries, while continuous cycling induces a structural transformation that allows greater accessibility to the inner regions of Fe-HHTP. These results provide a better understanding of the electrochemical and structural behavior of pristine MOFs that allow tailoring their properties for direct application in energy storage devices without the need for high-temperature processes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"10 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145432","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":"Synthesis and Characterization of Al and Si substituted Polyoxometalates","authors":"Jan-Christian Raabe, Saurabh Chitnis, Maximilian J. Poller","doi":"10.1039/d5dt00894h","DOIUrl":"https://doi.org/10.1039/d5dt00894h","url":null,"abstract":"Polyoxometalates with different transition-metals substituting the main framework element have recently been applied as promising catalysts. In comparison, polyoxometalates, featuring main-group elements in their framework are extremely rare. In this work, we present two main-group element substituted Keggin-type phosphotungstates containing Al or Si, and their characterization using spectroscopic and crystallographic methods. Al substituted POMs are rare examples, which means that the investigation of such systems deserves special attention. Guided by electronic-structure calculations, the reactivity of the Al substituted cluster with the electrophile benzyl bromide was investigated. This reactivity study together with the results of computational simulations illustrate new reaction behaviour for main-group element substituted polyoxometalates, setting the stage for future applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145430","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":"Ionic transport and luminescence properties in sodium- and fluorine-co-doped rare-earth molybdates NaLn4Mo3O15F (Ln = Sm–Tb)","authors":"Ekaterina Orlova, Yelizaveta A. Morkhova, Timofei A. Sorokin, Elena Yu Zakharova, Elena Kharitonova, Nikolay Viktorovich Lyskov, Roman Shendrik, Artem A Kabanov, V. O. Yapaskurt, Olga Alekseeva","doi":"10.1039/d5dt00809c","DOIUrl":"https://doi.org/10.1039/d5dt00809c","url":null,"abstract":"Halogenated rare-earth molybdates of the NaLn4Mo3O15F (Ln = Sm–Tb) nominal composition were synthesized via a solid-state route and investigated for their structural, thermal, IR spectroscopic, luminescent, and ionic transport properties. The study demonstrated that lanthanide cation size critically governs structural symmetry. Guided by symmetry analysis, Sm and Eu were prioritized for investigation as they stabilize the cubic fluorite-like framework, which exhibits superior ionic conductivity, whereas smaller cations (Gd, Tb) form low-conductivity monoclinic oxymolybdates. Fluorine incorporation and oxidative annealing significantly modulated oxygen interstitial content, as evidenced by lattice parameter variations and luminescence spectroscopy, which confirmed europium’s oxidation state transition (Eu2+ ↔ Eu3+). Here, the conductive properties of NaSm4Mo3O15F (NSMF) and NaEu4Mo3O15F (NEMF) were studied for the first time. Crystal chemical analysis of ionic conductivity revealed approximately equal oxygen migration barriers, with an estimated value of about 0.5 eV for 3D oxygen diffusion. The results of kinetic Monte Carlo simulations demonstrated oxygen ionic conductivity of about 10-2-10-3 S cm-1 at 800°C. To estimate the electronic contribution, density functional theory calculations were performed for band gaps calculations, which turned out to be ca. 0.6 eV. Conductivity measurements demonstrated a similar order of anionic conductivity, with enhanced electronic contributions under reducing conditions. Thermal analysis linked suppressed phase transitions in NSMF/NEMF to lattice rigidity caused by smaller lanthanides, contrasting with flexible lattices in MLn4Mo3O15F (M = Li, Na; Ln = La, Pr, Nd). These findings highlight fluorine’s role in tuning oxygen mobility and underscore the interplay between cation size, lattice dynamics, and conductivity for intermediate-temperature solid oxide fuel cell applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"50 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154104","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":"Sulfate-Modified MOF-808 as Superacid Catalysts: A Performance Evaluation of Zr(IV) and Hf(IV) Analogues in Acetalization Reactions","authors":"Vanesa Roa, Sebastian Cea, Cesar Pazo-Carballo, Jaime Llanos, Douglas Olivares, Nestor Escalona, Angel Leiva, Yoan Hidalgo-Rosa, Ximena Zárate, Ana Belén Dongil, Eduardo Schott","doi":"10.1039/d5dt00608b","DOIUrl":"https://doi.org/10.1039/d5dt00608b","url":null,"abstract":"In this study, we report the synthesis and characterization of MOF-808-SO₄-M (M = Zr(IV), Hf(IV)), derived from MOF-808-M precursors. The introduction of sulfate groups enhances the Brønsted acidity of these materials, significantly improving their catalytic performance in the benzaldehyde acetalization reaction. The materials were characterized using powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), nitrogen adsorption-desorption analysis, thermogravimetric analysis (TGA), energy dispersive spectroscopy (EDS), and Hammett indicator tests. The catalytic evaluation revealed that MOF-808-SO₄-Zr exhibited significantly higher conversion compared to its Hf-based analogue, a difference attributed to its greater density of acid sites, as confirmed by temperature-programmed surface reaction (TPSR) analysis. These experimental results were further supported by density functional theory (DFT) calculations, which provided insight into the acidic properties and catalytic behavior of the materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"18 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154105","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":"Ag(I) induced H-type and Pd(II) induced J-type phthalocyanines to enhance PDT applications: synthesis, optical behaviors, photochemical/photophysical properties, and DFT studies.","authors":"Elif Polat, Ahmet Turgut Bilgicli, Tenzile Alagöz, Hayriye Genç Bilgiçli, Hasan Pişkin, Burak Tuzun, Armağan Günsel, Ali Erdogmus, Meryem Nilüfer Yaraşır","doi":"10.1039/d5dt00590f","DOIUrl":"https://doi.org/10.1039/d5dt00590f","url":null,"abstract":"The literature shows that thiol compounds are important in various diseases, such as oxidative stress, enzymatic reactions, the respiratory system, metabolic disorders, and cancer. Thus, it is important to prepare derivatives of phthalocyanines, which have an important place in macrocyclic chemistry, substituted with biologically active thiol groups. Within the scope of this study, novel phthalonitrile derivative 3-(4-bromobenzylthio)phthalonitrile (1) and its metallophthalocyanine derivatives [ZnPc (2), CuPc (3), and CoPc (4)] were synthesized. The synthesized compounds were characterized by the combination of standard spectroscopic methods. The molecular structure of the synthesized phthalonitrile derivative and its related crystallographic features were determined by the single-crystal X-ray data analysis. The substitution with the thiol group of phthalocyanine molecules gives them high solubility features in organic solvents. Thus, the effect of self-aggregation behaviors on electronic spectra was determined in organic solvent media. Also, optical sensor properties in the presence of valuable metal ions were investigated by UV-Vis and fluorescence spectroscopy. Furthermore, the photochemical and photophysical properties of newly synthesized phthalocyanines were studied. Finally, the effect of Ag+ and Pd2+ ions on the singlet oxygen quantum yield was performed. According to the results, the newly synthesized ZnPc (2) is a good candidate for PDT as a photosensitizer. Also, the singlet oxygen quantum yield is highly improved in the presence of valuable metal ions such as Ag+ and Pd2+ ions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154275","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}