Dalton Transactions最新文献

{"title":"Charge optimization induces reconstruction via compounding Ni(OH)2 and CoP: a novel route to construct electrocatalysts for overall water-splitting","authors":"Hao Yin, Bingxian Wu, Xueyang Leng, Hong Gao, Jing Yao","doi":"10.1039/d5dt00056d","DOIUrl":"https://doi.org/10.1039/d5dt00056d","url":null,"abstract":"Electrolytic water-splitting has the advantages of high efficiency, environmental friendliness, and sustainability. It is becoming a leading approach for producing hydrogen. In order to improve the efficiency of water-splitting, a bifunctional electrocatalyst with high performance is needed. Herein, we present a novel approach to construct a bifunctional electrocatalyst for overall water-splitting by compounding Ni(OH)<small>₂</small> and CoP. This combination induced charge optimization, thereby leading to surface reconstruction. The nanocomposite displayed outstanding catalytic performance, benefiting from its more reactive surface area, improved conductivity and enhanced electrocatalytic activity. The resulting Ni(OH)<small>₂</small>/CoP electrocatalyst exhibited excellent catalytic performance, with low overpotentials of 266 mV at 50 mA cm<small>⁻²</small> for the OER and 71 mV at −10 mA cm<small>⁻²</small> for the HER, and required only 1.54 V to reach 10 mA cm<small>⁻²</small> in an overall water-splitting device, overtaking most of the recently reported Co- and Ni-based catalysts. This innovative strategy offers new directions for the design of efficient electrocatalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713426","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":"Divergent Reduction Chemistry of NHC-Aluminium(III) Hydrides","authors":"Fáinché Murphy, Alan Kennedy, Catherine Ellen Weetman","doi":"10.1039/d5dt00379b","DOIUrl":"https://doi.org/10.1039/d5dt00379b","url":null,"abstract":"Understanding and controlling facile reduction chemsitry is a key challenge in molecular main group chemistry. Herein, we report the divergent reduction chemistry of aluminium(III) hydrides supported by N-heterocyclic carbenes (NHCs). Choice of reducing agent and NHC ligand are key, with Al(II) dialanes, Al(II) cations, asymmetric Al(II) dialanes and ligand exchange reactions all identitifed via NMR and single crystal X-ray diffraction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"13 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703331","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":"Visible light compatible infrared stealth capability based on phase change materials","authors":"Zhou Ai, Huafeng Zhang, Shubo Cheng, Zao Yi, Qianju Song","doi":"10.1039/d5dt00311c","DOIUrl":"https://doi.org/10.1039/d5dt00311c","url":null,"abstract":"This paper utilizes thermochromic phase change materials VO2 and GST to design micro-nano structures with temperature-tunable thermal emission characteristics, further controlling their stealth effects in both visible light and infrared backgrounds. Initially, an infrared stealth structure based on GST is proposed. By exploring its crystalline (aGST) and amorphous (cGST) states, the optimal thickness of GST is determined to be 250 nm. The structures corresponding to aGST and cGST exhibit emissions of 0.24 and 0.24 respectively at the atmospheric window of 3-5 μm, and 0.03 and 0.15 at 8-14 μm. These low emission capabilities aid in achieving infrared stealth. In the non-atmospheric window of 5-8 μm, the emissions are 0.06 and 0.76, which can help reduce heat loss at low temperatures and radiate energy at high temperatures, thus optimizing the stealth effect. Subsequently, a ZnS layer is added on top to regulate structural color. By scanning the thickness of ZnS under different states of GST, we investigate the chromaticity coordinates of the structure in amorphous, crystalline, and mixed states with varying crystal proportions. From the perspective of infrared emissivity, the feasibility of visible light stealth is studied. A ZnS layer thickness of 150 nm is selected as the optimal parameter, determining the infrared emissivity for both states. The structures corresponding to aGST and cGST exhibit emissions of 0.17 and 0.22 at the atmospheric window of 3-5 μm, and 0.03 and 0.20 at 8-14 μm. The low emission capabilities help achieve infrared stealth, while the emissions within the non-atmospheric window of 5-8 μm are 0.10 and 0.77. Resonance absorption reasons are explained by calculating normalized electric field and energy dissipation intensity. Finally, a VO2 layer is added. Due to the reversible nature of the VO2 phase change, two phase change materials at different temperatures result in four states. The thickness of the VO2 layer is varied to explore the infrared emissivity under different states. This paper primarily focuses on designing dynamically tunable micro-nano structures by combining phase change materials, achieving precise control over reflection and emission characteristics in both visible light and infrared bands, thus providing more possibilities for stealth technology.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702899","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":"Solvent-directed assembly in MOFs with linear trinuclear cobalt(II) nodes: formation of inverted Figaro chains","authors":"Oluseun Akintola, Helmar Görls, Winfried Plass","doi":"10.1039/d5dt00149h","DOIUrl":"https://doi.org/10.1039/d5dt00149h","url":null,"abstract":"Four new cobalt(II) coordination networks based on the nitrilotribenzoic acid ligand (H<small>₃</small>ntb) with the formula {[Co<small>₃</small>(ntb)<small>₂</small>(solv)2]}<small>_<em>n</em></small> (where solv = dmf, def, dma, and EtOH), denoted as JUMP-4(solv), are reported. The trinuclear cobalt(II) clusters that constitute the three-dimensional network are coordinated by the six carboxylate groups of two bridging, deprotonated ntb<small>^3-</small> ligands. These clusters have two flexible coordination sites on the two terminal cobalt ions, which are partially saturated by the condensation of these clusters, leading to unprecedented inverted Figaro chains. Three of the frameworks were synthesized by combining cobalt(II) chloride and the ligand in a mixture of acetonitrile and the corresponding amide (dmf, def, and dma) in a 9:1 ratio, while the ethanol analogue could only be obtained by single-crystal-to-single-crystal transformation starting from the dmf and dma derivatives. The difference in the size of the solvents coordinated to the terminal cobalt(II) ions results in a pore-partitioning effect, as reflected in the argon sorption behavior of the networks. Magnetic measurements reveal antiferromagnetic interactions between the anisotropic cobalt(II) ions along the alternating inverted Figaro chains.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"215 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713425","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":"Micro-mechanism of Size Effect on the Deformation Homogeneity of Sb2Te3 Semiconductor","authors":"Qianqiu Liu, Runxi Jia, Xinlei Gao, Ben Huang, Guodong Li, Zhiguang Guo","doi":"10.1039/d5dt00343a","DOIUrl":"https://doi.org/10.1039/d5dt00343a","url":null,"abstract":"Sb2Te3 based semiconductor is the state-of-the-art commercial thermoelectric (TE) material at room temperature. To improve the performance stability of Sb2Te3 TE semiconductors and relevant applications in wearable devices, it is necessary to enhance their deformability. Although Sb2Te3 easily fractures along the weakly bonded Van der Waals (VdW) layers, the dislocation slip process on these layers can be facilitated by modulating the weak but reversible VdW bonds, implying the potential for improvement of the plastic deformation capacity. Here, taking structural homogeneity as the characteristic evaluation of the whole deformation process, the size effect of Sb2Te3 nanocrystals on the evolution of lattice defects and plastic deformation capacity is investigated by shear deformation in molecular dynamics. The results show that the influence of lattice distortion at the boundaries is weakened with the increasing structural size, which promotes the ordered breaking-reforming process of VdW bonds and alternating dislocation slips on VdW-coupled atomic layers. It reveals a close relationship between VdW bonds and defects during structural evolution, and therefore a microscale manner of energy dissipation and deformation coordination that is conducive to strain delocalization and fracture strain enhancement. This simulation work provides new insights into the plastic deformation mechanism of inorganic semiconductors given the effect of surface and crystal size, which will improve the defect engineering strategy for designing advanced TE semiconductors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702897","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 a novel copper carboxylate complex and a copper complex-coated polyether sulfone membrane for the efficient degradation of methylene blue dye under UV irradiation: Single crystal X-ray structure of copper carboxylate complex","authors":"Narinder Singh, Bulle Shah, Rupy Dhir, Ajnesh Singh","doi":"10.1039/d5dt00663e","DOIUrl":"https://doi.org/10.1039/d5dt00663e","url":null,"abstract":"Synthesis of a novel binuclear Cu (II) carboxylate complex under ambient laboratory conditions is presented. The complex possesses a paddle wheel structure in which the axial positions are occupied by bromide/nitrate ligands. The synthesized complex was characterized by single-crystal X-ray crystallographic, FT-IR, X-ray diffraction, and UV-Visible spectroscopic techniques. The thermal stability of the metal complexwas studied by the thermogravimetric analysis study. The synthesized metal complex was employed for the synthesis of metal complex-coated polyether sulfone (PES) membranes which were characterized before and after filtration using the FESEM technique. The photocatalytic efficiency of the metal complex was studied for the degradation of methylene blue dye under UV irradiation in the presence of H2O2 and was compared with the photodegradation efficiency of metal complex-coated polyether sulfone (PES) membrane.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695483","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":"New Supramolecular Tecton: The Crucial Impact of the Polycation Charge and Geometry of H-Bonds on the Structure and Properties of Halometallates in the Solid State","authors":"Tatiana Alekseevna Shestimerova, Alexey Medved'ko, Michael A. Bykov, Mikhail A Kalinin, Mikhail T. Metlin, Ilya V. Taydakov, Victoria E. Gontcharenko, Wei Zheng, Evgeny V. Dikarev, Sergey Z. Vatsadze, Andrei V Shevelkov","doi":"10.1039/d5dt00318k","DOIUrl":"https://doi.org/10.1039/d5dt00318k","url":null,"abstract":"New tricationic organic supramolecular tecton has been designed and synthesized. Contrary to known mono- and dicationic species, this new molecule, being a “three-way connector”, allows assembling infinite supramolecular sheets and nets upon interaction with appropriate inorganic counterpart complex anions. In this work, triprotonated 6-amino-5,7-dimethyl-1,3-diazaadamantane, comprising two secondary and one primary nitrogen atoms, is utilized as a trication to form hybrid compounds with iodometallate anions by exercising five hydrogen bonds at the time. It is shown that the bulky cation works simultaneously as a spacer and a connector, such that the positions of inorganic [MI6]3− anions (M = Sb, Bi) in the crystal structures are defined by five hydrogen bonds and are well-separated from each other. The latter is considered as a prerequisite for the hybrid compounds to display optical properties originating from the undisturbed electronic structure of individual inorganic anions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695484","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":"Heme-Aβ Compound 0: A Common Intermediate in ROS Generation and Peroxidase Activity","authors":"Chinmay Dey, Puja Pal, Soumya Samanta, Somdatta Ghosh Dey","doi":"10.1039/d5dt00234f","DOIUrl":"https://doi.org/10.1039/d5dt00234f","url":null,"abstract":"Oxidative stress is a key factor in neurodegenerative diseases, particularly in Alzheimer’s disease (AD) which is the leading cause of dementia. A hallmark of AD is the accumulation of amyloid β (Aβ) peptides, along with redox-active metal ions and heme cofactors, all of which significantly contribute to disease progression. When heme binds to Aβ, it can drive oxidative stress through two primary pathways: firstly, reduced high-spin ferrous heme-Aβ active site may generate H₂O₂ through oxygen reduction, leading to oxidation of biomolecules and lipid membranes; secondly, this H₂O₂ can react with oxidised form of high-spin ferric heme-Aβ, initiating peroxidase-like activity that can catalyse the oxidation of neurotransmitters. These pathways converge at a crucial intermediate i.e. the heme-Aβ-peroxo complex, or Compound 0, which serves as the final intermediate in the ROS cycle and the first in the peroxidase cycle. Although, we have previously characterized other intermediates in these pathways, Compound 0 resulting from the reaction of a high-spin heme-Aβ species with peroxides has remained elusive due to its rapid hydrolysis in an aqueous environment. In this study, we report the oxidation of dopamine by peroxides catalyzed by ferric heme-Ab species and successfully stabilised and characterized Compound 0 of high-spin heme-Aβ in dimethylformamide, an organic aprotic solvent. This stabilization enables detection through stopped-flow, EPR and resonance Raman spectroscopy, thereby facilitating a deeper understanding of the oxidative stress caused by high-spin heme-Aβ.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695544","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 biologically inspired iron complex for the homogeneous reduction of Cr(VI) to Cr(III).","authors":"Kelly L Gullett, Jewelianna M Moore, Courtney L Ford, Alison R Fout","doi":"10.1039/d5dt00416k","DOIUrl":"https://doi.org/10.1039/d5dt00416k","url":null,"abstract":"<p><p>Hexavalent chromium (Cr^VI) is a toxic and carcinogenic pollutant commonly found in industrial waste, posing significant environmental and health risks. In contrast, trivalent chromium (Cr^III) is significantly less toxic and less mobile in water. This study presents the efficient reduction of Cr^VI to Cr^III using a biologically inspired non-heme iron complex, [N(afa^Cy)₃Fe^IIOTf]OTf. The reaction achieves near-quantitative conversion as calculated by a paramagnetic ¹H NMR calibration method for direct quantification of the iron(III)-oxo species formed during reduction. X-ray photoelectron spectroscopy (XPS) confirms Cr^III as the final chromium containing product. This work provides a highly effective and selective approach to chromium detoxification, with potential applications in water remediation while demonstrating the utility of a ¹H NMR calibration curve for quantifying paramagnetic species in reaction mixtures.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699147","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":"Brightly emissive octahedral Cu4X4 clusters showing polymorphic-dependent and mechanochromic phosphorescence","authors":"Andrey Baranov, Irina Yu. Bagryanskaya, Marianna I Rakhmanova, Daria Metlina, Ilya V. Taydakov, Evgeniya Pavlovna Doronina, Alexander Artem'ev","doi":"10.1039/d5dt00103j","DOIUrl":"https://doi.org/10.1039/d5dt00103j","url":null,"abstract":"A series of [Cu4X4L2] clusters (X = Cl, Br, I) with an octahedral Cu4X4 core has been synthesized using bis(t-butyl)(2-pyridyl)phosphine (L1) and bis(2-pyridyl)-t-butylphosphine (L2). At room temperature, these clusters exhibit a bright 3(M+X)LCT phosphorescence (λmax = 514–570 nm) with the quantum yields up to 84% and lifetimes of 3–22 µs. Equally important, polymorphic-dependent and mechanochromic luminescence phenomena have been revealed for the first time for octahedral Cu4X4 clusters. Thus, two polymorphs of [Cu4Br4(L1)2] exhibit green and yellow-green phosphorescence with different emission efficiencies and lifetimes. The cluster [Cu4I4(L2)2] features two emission bands at 530 and 600 nm, which probably belong to 3(M+X)LCT and 3CC phosphorescence. When the powder of [Cu4I4(L2)2] is ground, these bands gradually merge into an averaged band at 575 nm, and when a small amount of CH3CN is added, the two original bands are recovered.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"96 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695546","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}