Dalton Transactions最新文献

{"title":"Interface engineering-triggered electronic regulation of ReS₂ and FeS₂ nanosheet arrays for high-performance electrochemical hydrogen evolution.","authors":"Guangyao Zhou, Bin He","doi":"10.1039/d6dt02187e","DOIUrl":"https://doi.org/10.1039/d6dt02187e","url":null,"abstract":"<p><p>Integrated compositional and morphological designs provide an effective strategy to optimize both thermodynamic and kinetic behaviors, thus enabling the construction of high-efficiency electrocatalysts. Herein, we develop ReS₂ and FeS₂ heterojunction nanosheet arrays arranged on a carbon cloth substrate (labeled as ReS₂/FeS₂@CC hereafter) through a one-step hydrothermal strategy. Experimental data demonstrated that the construction of heterojunctions and sheet-like arrays can freely reconfigure the electronic configuration, expedite charge transfer, and provide abundant reactive sites. Consequently, the ReS₂/FeS₂@CC electrode exhibits outstanding hydrogen evolution performance in an alkaline medium, with an overpotential of 109 mV, affording a current density of 10 mA cm^-2, a Tafel slope of 103.7 mV dec^-1 and long-term electrochemical stability in the <i>i</i>-<i>t</i> test for 56 h and the 4000-cycle test, thereby offering a promising method for sustainable and economical H₂ production.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134288","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":"Coordination engineering in antimony-based hybrid crystals toward highly efficient green emission.","authors":"Jiale Xu, Ruwei Song, Feiping Xiao, Yuecheng Xie, Jiejun Pan, Kaixuan Chen, Pingqi Gao, Jiancan Yu","doi":"10.1039/d6dt02163h","DOIUrl":"https://doi.org/10.1039/d6dt02163h","url":null,"abstract":"<p><p>Zero-dimensional organic-inorganic hybrid metal halides have emerged as promising luminescent materials with structural diversity and tunable emission properties. However, it remains challenging to precisely control the metal coordination environment to suppress non-radiative recombination and improve the photoluminescence quantum yield (PLQY). Herein, we report an acid-solvent synergistic strategy that enables stepwise evolution of Sb coordination environments in hybrid halides. The non-emissive phase (H₂PIP)[SbCl₅]·H₂O (1, PIP = piperazine), composed of edge-sharing [Sb₂Cl₁₀]^4- dimers, transforms into an orange-emitting intermediate (H₂PIP)₅(H₅O₂)[SbCl₅]₂[SbCl₆]Cl₄ (2) with mixed discrete polyhedra, in the presence of HCl. Upon CH₃CN incorporation, the mixed Sb coordination polyhedra transform into isolated [SbCl₆]^3- octahedra in green-emitting compound (H₂PIP)₂(NH₄)[SbCl₆]Cl₂·CH₃CN (3). Accompanying this evolution of coordination environments, the PLQY rises from <1% to 23.6% for the intermediate and ultimately reaches 90.4%. The enhanced PLQY originates from the expanded Sb⋯Sb distance and significant [SbCl₆]^3- octahedral distortion, which facilitate the formation and radiative recombination of self-trapped excitons. This work provides insights into acid-solvent directed coordination engineering for highly efficient Sb-based hybrid emitters.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134308","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 catalytic performance of Au_<i>n</i>Pd_<i>n</i> (<i>n</i> = 1-4, 10) clusters for the Buchwald-Hartwig reaction.","authors":"Shu-Ying Huang, Zhi-Chao Zhang, Hai-Yan Zhong, Wei-Ming Sun","doi":"10.1039/d6dt01890d","DOIUrl":"https://doi.org/10.1039/d6dt01890d","url":null,"abstract":"<p><p>The C-N coupling reaction, namely the Buchwald-Hartwig coupling reaction, is a pivotal transformation in medicinal chemistry, and thus, the development of efficient catalysts for this process is of great importance. In this study, the catalytic performance of bimetallic Au_<i>n</i>Pd_<i>n</i> (<i>n</i> = 1-4, 10) clusters for the Buchwald-Hartwig coupling reaction has been investigated by density functional theory (DFT). Our results demonstrate that the catalytic activity of Au_<i>n</i>Pd_<i>n</i> (<i>n</i> = 1-4) clusters gradually increases as the cluster size increases. Hence, the catalytic mechanism of a larger Au₁₀Pd₁₀ cluster for the Buchwald-Hartwig (BH) reaction was further examined, and it was found that Au₁₀Pd₁₀ exhibits excellent catalytic performance for this C-N coupling reaction. The difference in the catalytic activity of these Au_<i>n</i>Pd_<i>n</i> (<i>n</i> = 1-4, 10) clusters for the BH reaction has been understood by analyzing their electronic structures and charge transfer. This work provides theoretical insights into the design of bimetallic cluster catalysts for C-N cross-coupling reactions and highlights the potential of such clusters as catalytic platforms with tunable performance for various organic coupling reactions.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134295","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":"Preparation of [Co(II)(PNNP)Br]⁺ PNNP = {PR¹₂CH₂CHNCHR²-}₂ complexes by the template method and their reactions.","authors":"Renee G Eleftheriades, Alan J Lough, Paul A Dube, Robert H Morris","doi":"10.1039/d6dt01732k","DOIUrl":"https://doi.org/10.1039/d6dt01732k","url":null,"abstract":"<p><p>Paramagnetic cobalt(II) and diamagnetic cobalt(III) PNNP complexes were prepared for the first time from bench-stable phosphonium dimers in a facile one-pot template synthesis. The template method allows for the easy customization of the phosphine and amine backbone substituents. Smaller substituents and anions result in the formation of unusual polymeric structures featuring linear bromide bridges. These complexes were characterized by crystallography, elemental analysis, cyclic voltammetry, magnetometry and electron paramagnetic resonance spectroscopy. The PNNP ligands impart similar electrochemical properties to Co(II) as the (PMe₂CH₂CH₂PMe₂)₂ ligand set according to a modified Lever correlation. The complexes undergo interesting redox disproportionation reactions. They are less active for the catalytic transfer hydrogenation of ketones than similar complexes with an NH group on the PNNHP' ligand.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134274","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":"2,2'-Dithiotolane pincer ligands with an electronically non-innocent central π-CC ligating unit and their coordination chemistry to transition metals.","authors":"Benjamin Rudin, Lukas Eberle, Carsten Wolf, Joachim Ballmann, Lutz H Gade","doi":"10.1039/d6dt02224c","DOIUrl":"https://doi.org/10.1039/d6dt02224c","url":null,"abstract":"<p><p>The synthesis of a family of 2,2'-dithiotolane ligands with different substitution patterns is reported. The ligands feature an electronically non-innocent alkyne backbone with two thioether donor arms in the wing-positions. This enables pincer-type coordination to early and mid transition metals, as shown for tantalum, molybdenum, rhenium, and ruthenium. The resulting complexes exhibit subtle yet distinct differences in reactivity, demonstrating the electronic adaptability of the pincers and highlighting their potential as ancillary ligands for transition metals. Furthermore, the reduction of selected molybdenum complexes was explored, revealing a pronounced tendency towards dimerisation and enabling the isolation and characterisation of two constitutional isomers featuring Mo-Mo bonding. The latter was further elucidated by quantum-chemical modelling.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134167","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":"A physically consistent framework for microstructural and optical characterization of spinel ferrite nanoparticles: insights from Mn_0.7Co_0.3Fe₂O₄.","authors":"Tran Thi Ngoc Nha, Minh Cong Tran, Dang Ngoc Toan, Dinh Thanh Khan, Le Thi Tuyet Ngan, P T Tho, Pham Thanh Phong","doi":"10.1039/d6dt01971d","DOIUrl":"https://doi.org/10.1039/d6dt01971d","url":null,"abstract":"<p><p>This work presents a comparative methodology for assessing the reliability of microstructural and optical parameters derived from different analytical models, using thermally decomposed Mn_0.7Co_0.3Fe₂O₄ nanoparticles as a model system. Fourier-transform infrared spectroscopy confirmed the formation of the spinel ferrite structure, with characteristic tetrahedral and octahedral vibration bands at 550 and 432 cm^-1, respectively. Rietveld refinement established a single-phase cubic spinel structure, while transmission electron microscopy revealed a relatively narrow particle-size distribution with an average diameter of 6.5 nm based on 319 particles. EDX elemental mapping showed a relatively homogeneous spatial distribution of Co, Mn, Fe, and O, with no detectable elemental segregation within the spatial resolution and detection limits of the measurement. To ensure reliable X-ray line-profile analysis, instrumental broadening was calibrated under identical experimental conditions using the certified NIST SRM 660c (LaB₆) standard. Although the Lorentzian and Gaussian limiting assumptions of the Williamson-Hall method produced markedly different microstructural parameters, the Size-Strain Plot and Halder-Wagner methods converged to nearly identical crystallite sizes (∼6.7 nm) with excellent linearity (<i>R</i>² > 0.99). The corresponding microstrain values of (0.58-1.43) × 10^-3 indicate weak lattice distortion, while the close agreement between the TEM particle size and XRD crystallite size suggests predominantly single coherently diffracting domains. Optical analysis yielded band-gap energies of 2.46 and 2.62 eV from the Kubelka-Munk and Kramers-Kronig formalisms, respectively, demonstrating the influence of dispersion effects on diffuse-reflectance analysis. The low Urbach energy (0.047 eV) is consistent with the weak lattice microstrain, indicating a limited degree of both structural and electronic disorder. These results demonstrate that reliable nanoscale parameters depend critically on instrumental calibration and analytical-model selection, highlighting the importance of physically consistent diffraction and optical modeling for the characterization of nanocrystalline spinel ferrites.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149126067","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":"<i>In situ</i> alkaline etching of MIL-100(Fe) to NiFe-layered double hydroxide nanosheets for electrocatalytic oxygen evolution.","authors":"Tian Zhao, Xing Zhang, Fuli Luo, Jiayao Chen, Yan Wu, Tianhang Wang, Ying Chen, Yi Chen","doi":"10.1039/d6dt01861k","DOIUrl":"https://doi.org/10.1039/d6dt01861k","url":null,"abstract":"<p><p>The development of efficient and durable non-noble metal electrocatalysts toward the oxygen evolution reaction (OER) is critical for the high-efficiency storage of renewable energy. Herein, a facile and controllable sacrificial template strategy is reported. Using MIL-100(Fe) as the sacrificial template under alkaline conditions, a series of NiFe-LDH electrocatalysts are fabricated by regulating the feeding amount of the nickel source, to explore the influence of Ni/Fe molar ratio on the OER electrocatalytic performance. Systematic characterization studies and electrochemical tests reveal that the optimized NiFe-LDH delivers an overpotential of 242.2 mV at 10 mA cm^-2 together with a Tafel slope of 36.67 mV dec^-1, surpassing commercial IrO₂ and exhibiting remarkable long-term stability. Such outstanding electrocatalytic performance originates from the synergistic electronic interaction between Ni and Fe sites, which optimizes the adsorption energy of reaction intermediates and accelerates the reaction kinetics. This work not only offers a high-performance OER electrocatalyst, but also provides a versatile sacrificial template strategy for constructing advanced multimetallic electrocatalysts.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134210","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":"Modular late-stage vectorization of Fe(II)-terpyridine complexes for photoacoustic and photothermal applications.","authors":"Malvyna Venne, Antoine C Gravet, Stéphanie Philippot, Mathilde Bouché","doi":"10.1039/d6dt01865c","DOIUrl":"https://doi.org/10.1039/d6dt01865c","url":null,"abstract":"<p><p>The development of vectorized molecular photothermal agents is often limited by the lack of modular synthetic strategies that allow the introduction of biological vectors without compromising the properties of the previously engineered agents. Herein, we report a late-stage vectorization synthetic strategy where pyridinium quaternization of a preformed Fe(II)-terpyridine complex provides a straightforward and versatile access to libraries of vectorized agents while preserving their intrinsic photophysical and photothermal properties. This Fe(II)-terpyridine complex was used as a common synthetic intermediate for the final step introduction of biotin vectors bearing different linkers to afford the desired bis-vectorized complexes. Importantly, the quaternization strategy was designed to enhance the electron-withdrawing character of the ligand, hence reducing the energy of the metal-to-ligand charge-transfer transition for red shifting it toward the near-infrared region, thereby making them relevant for irradiation in photobiology. Beyond enhancing these previously engineered optical properties, late-stage vectorization substantially improved the <i>in vitro</i> biological behavior of the complexes. The vectorized complexes displayed enhanced cellular accumulation, confirmed by photoacoustic imaging, together with negligible <i>in vitro</i> dark toxicity, efficient photothermal conversion and cytotoxicity under irradiation, while maintaining high chemical and photostability. Overall, this work establishes late-stage functionalization by quaternization of a pre-formed Fe(II)-terpyridine complex as a modular design strategy to decorrelate functionalization with a vector as the final synthetic step from engineering the photothermal core, for producing performant vectorized Fe(II)-based agents active in photoacoustic imaging and photothermal therapy.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149126117","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":"How native metal-binding sites accommodate uranyl: a comparative study of human serum transferrin, human serum albumin, and an engineered uranyl-binding protein.","authors":"Marek Freindorf, Elfi Kraka","doi":"10.1039/d6dt01933a","DOIUrl":"https://doi.org/10.1039/d6dt01933a","url":null,"abstract":"<p><p>Understanding how the uranyl ion (UO₂²⁺) exploits native metal-binding sites in human proteins is essential for elucidating uranium transport, accumulation, and toxicity. In this computational study, we investigated how uranyl is accommodated within the protein pockets of human serum transferrin and human serum albumin, and compared these interactions with those in an engineered super uranyl-binding protein (SUP). QM/MM geometry optimizations and harmonic vibrational frequency calculations were performed starting from available X-ray crystal structures. The intrinsic strengths of individual uranyl-protein interactions were quantified using Local Vibrational Mode Analysis (LMA), complementary with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) analyses. Histidine residues form the strongest individual U-N interactions, whereas aspartate and glutamate provided equally strong or stronger capture through bidentate U-O coordination. In human serum transferrin, the native carbonate cofactor forms an important component of the uranyl coordination sphere, whereas hydrogen bonds involving the uranyl oxo atoms contributed only weakly to binding. Comparison with the high-affinity SUP revealed that human serum proteins bind uranyl nearly as strongly as the engineered protein, highlighting their potential role in uranium transport and fate following human exposure.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134299","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":"Surface strain-regulated interfacial catalysis in Pd₃Pb nanosheets for enhanced C1-pathway ethanol electrooxidation.","authors":"Haoyu Sun, Yingying Wang, Yanyun Ma, Yiqun Zheng","doi":"10.1039/d6dt02114j","DOIUrl":"https://doi.org/10.1039/d6dt02114j","url":null,"abstract":"<p><p>Intermetallic palladium-based nanomaterials hold great promise for alcohol electrooxidation, but the role of surface topography in governing interfacial catalytic processes remains underexplored. Herein, we report a comparative investigation of intermetallic Pd₃Pb nanosheets with flat and crumpled surface topographies, where the crumpled morphology is achieved by introducing <i>N</i>-(octadec-9-en-1-yl)diethanolamine during synthesis, while flat nanosheets are obtained in its absence. For ethanol oxidation, the crumpled Pd₃Pb nanosheets deliver a mass activity of 1742.9 mA mg^-1 and retain 10.0 mA cm^-2 after 100 cycles, substantially outperforming flat nanosheets (1192.8 mA mg^-1, 3.4 mA cm^-2) and commercial Pd/C (709.2 mA mg^-1, 1.1 mA cm^-2). <i>In situ</i> Raman spectroscopy reveals that the reaction proceeds predominantly <i>via</i> the C1 pathway, evidencing efficient C-C bond cleavage on the crumpled surface. By using density functional theory simulations this enhancement can be attributed to localized surface strain induced by the crumpled topography-modeled on the Pd₃Pb(311) surface-which upshifts the d-band center to -1.53 eV and strengthens *OH binding (-3.29 eV), thereby optimizing intermediate adsorption energetics and facilitating the oxidative removal of carbonaceous poisons. This work provides a synthetic route to engineer crumpled surface topography in intermetallic nanosheets and demonstrates its critical role in regulating interfacial catalysis for C1-selective alcohol electrooxidation.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134343","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}