Dalton Transactions最新文献

{"title":"Reactivity of molybdenum–nitride complex bearing NHC-based PCP-type pincer ligand toward unsaturated substrates","authors":"Tomoyuki Miyazaki, Shun Suginome, Taiji Nakamura, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi","doi":"10.1039/d5dt02036k","DOIUrl":"https://doi.org/10.1039/d5dt02036k","url":null,"abstract":"Reactivity of a molybdenum–nitride complex bearing an N-heterocyclic carbene (NHC)-based PCP-type pincer ligand (1), whose nitride ligand is derived from dinitrogen, toward various unsaturated substrates was systematically investigated. The reaction of complex 1 with carbon monoxide as a substrate featuring a C–O triple bond afforded the corresponding cationic nitride–carbonyl complex, where the carbonyl ligand is coordinated to the molybdenum centre in place of the iodine ligand. Reactions of complex 1 with 1-pentyne, ethylene, and maleic anhydride as substrates featuring a C–C multiple bond afforded the corresponding π-complexes, where the C–C multiple bond is coordinated to the molybdenum centre. The reaction of 1 with dioxygen also yielded the corresponding π-complex in a similar manner to the reaction with ethylene. Finally, we investigated the redox reactivities of nitride–carbonyl and nitride–alkyne complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189115","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":"Structurally Modified Dipyrazinylpyridine-Based Homoleptic Cu(II) Complexes: Comparative Cytotoxic Evaluation in Breast Cancer Cell Lines","authors":"Indrajit Roy, L. Karthikeyan, Sourav Deb, Sharan Shanmuga Vuppaladadium Rathnam, Jitender Jangra, Snehashish Patra, Anindya Roy, Somnath Maji","doi":"10.1039/d5dt01877c","DOIUrl":"https://doi.org/10.1039/d5dt01877c","url":null,"abstract":"The DNA interaction ability of transition metal complexes is closely related to the ligand structure, which plays a crucial role in therapeutic applications. In this context, two mononuclear homoleptic Cu(II) complexes, [Cu(L1 ) 2 ](ClO 4 ) 2 , 1 and[Cu(L2) 2 ](ClO 4 ) 2 , 2 (Where, L1 = 4-(2,6-di(pyrazin-2-yl)pyridin-4-yl)-N,N-dimethylaniline and L2 = 4-(2,6di(pyrazin-2-yl)pyridin-4-yl)-N,N-diphenylaniline), were synthesised and characterised using various spectroscopic and analytical techniques. SCXRD data indicate that in both complexes the central Cu(II) unit is oriented in a distorted octahedral manner. The redox performance of the complexes was investigated using various voltammetric techniques. The DNA-binding ability of the complex was investigated using absorbance spectroscopy and ethidium bromide (EB) fluorescence quenching studies with double-stranded salmon sperm DNA (ss-DNA). The binding constant (K b ) and the Stern-Volmer constant (Ksv) were obtained in the range of 10 4 M -1 . Molecular docking studies were performed to gain knowledge about the interaction between B-DNA and the complexes. Furthermore, DNA nicking activity was monitored by in vitro electrophoresis analysis of supercoiled plasmid DNA. The effect of cell viability on MCF-7 and MDA-MB-231 cell lines was investigated. Cellular production of reactive oxygen species (ROS) was determined using a fluorescent probe (Calcein-AM). Notably, co-administration of 1 with Camptothecin (CPT) enhanced the overall cytotoxic effect, suggesting a synergistic therapeutic response. Interestingly, these results could lead to the development of cost-effective non-platinum transition metal-based chemotherapeutic agents to overcome the lacuna of the present conventional drugs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189118","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":"Indications of Ferroelectric Behaviour Near Room Temperature in the Organic–Inorganic Hybrid Q₂CuBr₄","authors":"Agnieszka Cizman, Dorota A. Kowalska, Paweł Szarek, Wojciech Medycki, N. A. Wojcik, Marek A. Gusowski, Monika Trzebiatowska, Adam Bartosiewicz, Liudmyla Filevska, Piotr Staniorowski, Ewelina Jach","doi":"10.1039/d5dt01668a","DOIUrl":"https://doi.org/10.1039/d5dt01668a","url":null,"abstract":"A quinuclidinium-based copper bromide molecular ferroelectric, exhibiting a spontaneous polarization of Ps = 0.52 μC/cm², has been successfully synthesized. This compound undergoes an order–disorder phase transition at Tc = 295 K, associated with thermally induced rotational motion of the quinuclidinium cations. This transition results in pronounced changes in both the dielectric constant and thermal properties. The contributions of the organic and inorganic components, as well as their interactions, to the observed electrical and thermal behaviors are discussed using both experimental data and theoretical analysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189119","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":"High-Sensitivity Optical Thermometry with Cr³⁺-Doped Hybrid Formate Perovskites: Comparative Analysis of Ratiometric and Lifetime-Based Approaches","authors":"Adam Kabański, Kacper Caputa, Dagmara Stefanska","doi":"10.1039/d5dt01748c","DOIUrl":"https://doi.org/10.1039/d5dt01748c","url":null,"abstract":"Optical thermometry, due to its properties such as rapid response, usability, high sensitivity, and remote measurements—is gaining increasing interest among researchers. Particularly promising materials for low-temperature thermometry applications are metal-organic frameworks (MOFs) containing chromium(III) ions. In this work, we present a method for optimising data for the development of a temperature sensor, with particular focus on the relative sensitivity parameter (Sr). As part of the optimisation process, we distinguish two approaches using different data analysis techniques and observe the impact of individual parameters on the temperature characteristics of the materials. Additionally, we present the structural and spectroscopic properties of a series of [EA]MgxCr1-x(HCOO)3, where EA = ethylammonium cation, and x = 0, 0.01, 0.03, and 0.05. These materials are characterised by a perovskite structure and exhibit a strong dependence of spectroscopic properties on the concentration of the dopant and temperature. The luminescent properties of chromium(III) ions change due to variations in the crystal field strength (Dq/B), which is measured using diffuse reflectance spectroscopy and photoluminescence techniques. Investigated materials exhibit particular temperature-dependent luminescence, which can be implemented as a basis for the thermometric model determination. Moreover, the influence of temperature on luminescence lifetime provides secondary thermometric pathway, what has not been reported for hybrid formate perovskites before. Obtained optical ratiometric sensors are characterized by high relative sensitivity (up to 3.07%∙K-1 at 130 K) and wide operating range (up to 80-170 K interval). Presented thermometric analysis of the lifetime-based model shows high relative sensitivity up to 2.97%∙K-1 (140 K). In this work, we investigate the influence of the chemical composition on observed thermometric performance within a series of EA-based hybrid compounds and compare two thermometric approaches – ratiometric and lifetime-based. What is more, we provide a comprehensive comparison of the spectroscopic properties, especially concerning the thermometric potential, with other reported hybrid formates, differing in a type of the organic cation. Presented results show a particular potential of hybrid formate perovskites doped with Cr3+ ions, especially within the context of highly sensitive luminescent thermometry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"67 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183178","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":"Ligand-Protected Silver-Sulfur and Cadmium-Sulfur Clusters: Structures and Transformations","authors":"Xinyu Tong, Yi-Jing Zeng, Yan-Xiang Ling, Ju-Suo Zhong, Zhan-Guo Jiang, Cai-Hong Zhan","doi":"10.1039/d5dt02085a","DOIUrl":"https://doi.org/10.1039/d5dt02085a","url":null,"abstract":"Silver-sulfur (Ag-S) and cadmium-sulfur (Cd-S) clusters, serving as critical bridges linking simple chalcogenides to semiconductor nanoparticles, have emerged as research hotspots in nanomaterials due to their unique optoelectronic properties, atomically precise structures, and controllable functionality. This review systematically summarizes the structural characteristics and transformation mechanisms of ligand-protected Ag-S and Cd-S clusters. Structurally, both are zerodimensional semiconductor nanomaterials with specific metal-sulfur stoichiometries and 4d 10 electron configurations, yet exhibit significant differences in metal ion characteristics, bonding interactions, and symmetry. Ligands regulate cluster size, stability, and optoelectronic properties through coordination. Regarding transformation mechanisms, structural transitions in Ag-S clusters can be achieved via electrochemical driving, ligand mediation, and sulfur source modulation, while Cd-S clusters primarily undergo transformations through ion exchange, temperature/ligand-induced isomerization, and ligand treatment.These findings provide key theoretical foundations for understanding nucleation mechanisms in semiconductor nanomaterials and designing functional cluster materials. Their application potential in optoelectronics, catalysis, bioimaging, and related fields further lays the groundwork for developing next-generation functional nanomaterials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"10 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183179","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":"Design of titanium-oxide cluster-based metal-covalent organic frameworks for efficient photocatalytic CO2 reduction.","authors":"Teng Liu,Yao-Mei Fu,Xing Meng,Li Xue,Hai-Ning Wang,Zhong-Min Su","doi":"10.1039/d5dt01871d","DOIUrl":"https://doi.org/10.1039/d5dt01871d","url":null,"abstract":"In response to the growing global energy requirements and escalating environmental issues, photocatalytic reduction of CO2 has gained significant attention as an effective strategy for carbon resource reutilization and addressing climate change. In this study, a series of metal-covalent organic frameworks (MCOFs) incorporating titanium-oxide clusters (Ti6) were systematically designed and synthesized. By tuning the Ti6 incorporation ratio, MCOF-TDT was found to exhibit an outstanding CO generation rate with the highest formation rate of 168 μmol g-1 h-1. To further enhance the practical applicability of the photocatalyst, a MCOF layer was grown on a pre-synthesized Ti6/PVDF substrate, successfully yielding MCOF-TDT/PVDF composite membranes, which achieved a CO generation rate of 78 μmol g-1 h-1. The incorporation of the PVDF substrate significantly improved the mechanical stability of the membrane while preserving much of its photocatalytic activity. This study presents a novel strategy for designing high-performance, stable photocatalytic materials and broadens the application scope of titanium-oxide cluster-based MCOFs in photocatalysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"106 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182871","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":"Lanthanide complexes bearing a bioinspired CuII binding site with picomolar affinity: synthesis, structural, relaxometric and luminescence studies.","authors":"Katharina Zimmeter,Bertrand Vileno,Agnès Pallier,Carlos Platas-Iglesias,Peter Faller,Célia S Bonnet,Angélique Sour","doi":"10.1039/d5dt01735a","DOIUrl":"https://doi.org/10.1039/d5dt01735a","url":null,"abstract":"In the pursuit of CuII-responsive MRI contrast agents with enhanced CuII affinity, we report the synthesis and characterization of two LnIII-DO3A-C3AmpicGH complexes (LnIII = GdIII, EuIII), featuring a tetradentate CuII-binding moiety, along with the corresponding mononuclear CuII-C3AmpicGH complex. The chelator coordinates CuII through two amide groups, a pyridine and an imidazole ring. The use of a propyl-amide linker between the LnIII- and CuII-binding moieties allowed an increased separation between the two metal centers. As a result, both LnIII-CuII-DO3A-C3AmpicGH and CuII-C3AmpicGH complexes exhibit the same CuII-affinity (log K = 11-12 at pH 7.4) and good selectivity over competing physiological metal ions, particularly ZnII (up to at least 500 equivalents). While the GdIII complex displayed no relaxivity changes upon CuII binding, the EuIII analogue showed a luminescence turn-off response. Spectroscopic analyses as well as density functional theory (DFT) calculations provide insights into the coordination environments of both metal ions, notably confirming the absence of amide coordination to the LnIII center, even in absence of CuII.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"66 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182543","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":"Mixed ligand Cu(II) complexes as new precursors for the synthesis of CuO nanomaterials: development of homogeneous and heterogeneous catalysts for styrene epoxidation and phenol hydroxylation under mild conditions.","authors":"Mitu Sharma,Mukesh Sharma,Sazida Yasmin Sultana,Mallayan Palaniandavar,Nashreen S Islam","doi":"10.1039/d5dt01420d","DOIUrl":"https://doi.org/10.1039/d5dt01420d","url":null,"abstract":"A new synthetic strategy for obtaining CuO nanocatalysts has been devised using a pair of newly synthesized mixed ligand Cu(II) complexes as the precursors. The new Cu(II) complexes are of the types [Cu(def)(bpy)(NO3)] 1 and [Cu(def)(phen)(H2O)]NO3·(CH3OH) 2, where def (deferiprone) is the primary ligand and bpy (2,2'-bipyridine) and phen (1,10-phenanthroline) are the co-ligands. They have been employed as the synthetic precursors for the straightforward synthesis of CuO nanomaterials. The single crystal X-ray structures of 1 and 2 reveal that both the complexes possess square pyramidal coordination geometries. The mixed ligand-templated CuO nanomaterials 3 and 4 have been obtained via thermal degradation of the complexes 1 and 2, respectively. They have been comprehensively characterized using FT-IR, UV-DRS, XRD, SEM, TEM, and BET analyses. The CuO nanocomposites have been found to be efficient heterogeneous catalysts for the selective styrene epoxidation with H2O2, yielding a striking 99.7% conversion and 99.3% selectivity under organic solvent-free conditions. Also, the same nanocatalysts displayed remarkable efficiency as water tolerant heterogeneous catalysts to facilitate phenol hydroxylation (65.9/67.8% conversion) with H2O2 in aqueous medium. They could be easily recovered and recycled for at least three consecutive cycles without significant lowering of their selectivity or activity profile. The precursor mixed ligand complexes 1 and 2, on the other hand, served as homogeneous catalysts in the epoxidation of styrene under similar solvent-free reaction conditions with 98.5/97.3% conversion and around 99% selectivity, as well as in the phenol hydroxylation in aqueous medium with 63.2/69.3% conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"96 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182870","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":"NiFeCe nanosheet arrays by N and P doping as efficient electrocatalysts for oxygen evolution reaction","authors":"Chao Xu, Dan Wu, Qiangqiang Wang, Xuan Kuang, Xu Sun, Xiang Ren, Qin Wei","doi":"10.1039/d5dt01787d","DOIUrl":"https://doi.org/10.1039/d5dt01787d","url":null,"abstract":"The oxygen evolution reaction (OER) is commonly considered to be the major bottleneck in electrochemical water splitting, characterized by high overpotential requirement, so the fabrication of low cost and high-performing OER catalyst is of great significance for the process of electrocatalytic water splitting. Here, the nanocomposite material (denoted as N-Ni 0.75 Fe 0.15 Ce 0.10 P/NF) was obtained by simultaneously nitriding and phosphating the nanoneedle-like array (denoted as Ni 0.75 Fe 0.15 Ce 0.10 O x /NF) grown on nickel foam(NF). N-Ni 0.75 Fe 0.15 Ce 0.10 P/NF has an overpotential of only 244 mV at a current density of 50 mA cm -2 . In addition, the Tafel slope is remarkably low at 73.8 mV dec -1 . The material can work stably at a current density of 50 mA cm -2 for at least 48 h, indicating good stability. This investigation introduces innovative design methodologies for OER catalysts, offering significant contributions to sustainable energy research.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"97 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183177","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":"Constructing MOF-on-MOF heterojunction on hematite photoanode for efficient photogenerated carrier transport","authors":"Yuhan Bai, Xiu-Shuang Xing, Mengshuo Yin, Wenting Zhang, Shaomei Wang, You-Juan Zhang, Zhongyuan Zhou, Jimin Du","doi":"10.1039/d5dt01814e","DOIUrl":"https://doi.org/10.1039/d5dt01814e","url":null,"abstract":"The effective construction of surface catalyst and heterojunction can accelerate photogenerated carrier separation and transfer to further improve photoelectrochemical water splitting (PEC-WS) performance. Integration of two or more metal-organic frameworks (MOFs) as surface overlayers onto photoelectrode materials can build a nanoscale MOF-on-MOF heterojunction to drive the separation and transfer of photogenerated electron-hole pairs. In this work, MIL-96 and UiO-66 MOFs are sequentially loaded onto α-Fe<small>₂</small>O<small>₃</small> photoanode by a strong interaction to form an effective MOF-on-MOF heterojunction, which exhibits excellent PEC catalytic activity and stability. The α-Fe<small>₂</small>O<small>₃</small>/MIL-96/UiO-66 photoanode exhibits a 125% enhancement of photocurrent density (2.25 mA/cm<small>²</small>) at 1.23 V<small>_RHE</small>. The coexistence of Fe<small>³⁺</small>/Fe<small>²⁺</small> and O<small>_V</small> can enhance the electric conductivity and reduce charge recombination rate of α-Fe<small>₂</small>O<small>₃</small> photoanode. The formation of Fe-O/Fe and weak Fe-Al(MIL-96) and Fe-Zr(UiO-66) coordination facilitates photogenerated electron-hole transport between α-Fe<small>₂</small>O<small>₃</small> photoanode and MIL-96/UiO-66 overlayer. Furthermore, the constructed bimetallic MIL-96/UiO-66 heterojunction synergistically provides more active sites, and promotes photogenerated carrier separation and transfer, finally effectively reducing the reaction kinetics of water oxidation and enhancing the PEC-WS performance. This work provides a new modifying route to develop the high-efficiency photoelectrode materials with outstanding PEC-WS performance.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"91 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141012","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}