Dalton Transactions最新文献

{"title":"Bimetallic platinum(II) complexes with bridging di-NHC and N^C^C ligands: synthesis and photophysical properties","authors":"Mariano Paredes, Dionisio Poveda, Pablo González-Herrero, Ángela Vivancos","doi":"10.1039/d5dt01761k","DOIUrl":"https://doi.org/10.1039/d5dt01761k","url":null,"abstract":"Three new bimetallic Pt(<small>II</small>) compounds of the type [{Pt(dmtppy)}<small>₂</small>{μ-(Im<small>_Me</small>)<small>₂</small>(CH<small>₂</small>)<small>_<em>n</em></small>}] [<em>n</em> = 1 (<strong>1</strong>), 3 (<strong>2</strong>), 6 (<strong>3</strong>)], where dmtppy is the dimetalated tridentate N^C^C ligand 2-(4,4′′-dimethyl-[1,1′:3′,1′′-terphenyl]-5′-yl)pyridine and Im<small>_Me</small> is <em>N</em>-methylimidazol-<em>N</em>-yl-2-ylidene, have been synthesized in order to explore their ability to form molecular assemblies that affect their luminescence. Restricted rotation around the Pt–carbene bond leads to mixtures of atropisomers, which hinder the growth of single crystals. The complexes show efficient emissions with high phosphorescence quantum yields in 2 wt% doped PMMA films at 298 K (PLQY: 73–77%). Significant modifications of their photophysical properties in fluid solution are observed upon variation of the solvent, with the highest efficiencies found in 2-methyltetrahydrofurane (up to 63% quantum yield for complex <strong>3</strong>). In the case of complex <strong>1</strong>, which contains the shortest linkage, the formation of excimers in MeCN and MeOH causes a significant quenching of the emission, with a substantial decrease in the quantum yield.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"53 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203197","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":"Dual Functioning Ru(II)/Ir(III) Complexes for Ferroptosis and Apoptosis in Triple Negative Breast Cancer: A Proof of Concept by Glutathione Depletion","authors":"Utpal Das, Tiasha Dasgupta, Krishna Santhoshkumar, Jayaprakash Meena, Annamalai Senthil Kumar, Rajesh Kushwaha, Rishav Das, Debasish Mondal, Kuntal Maji, Prasanta Ghosh, Samya Banerjee, Tamizhselvi Ramasamy, Rinku Chakrabarty, Priyankar Paira","doi":"10.1039/d5dt01428j","DOIUrl":"https://doi.org/10.1039/d5dt01428j","url":null,"abstract":"Triple-negative breast cancer (TNBC) is the most aggressive subtype of breast cancer which lacks effective targeted therapies because of negative expression of the targetable bioreceptors. Fighting with TNBC requires innovative solutions beyond conventional treatments. Herein, we have introduced novel imidazo-phenanthroline-based Ru(II)/Ir(III) complexes that exhibit a dual function on cancer cells by triggering both apoptosis and ferroptosis. By generating a surge of reactive oxygen species (ROS), depleting crucial antioxidants like GSH (Glutathione) and NADPH (nicotinamide adenine dinucleotide phosphate), and disrupting mitochondrial function, these complexes dismantle tumor defenses from within. Mechanistically, these complexes disrupt the antioxidant defense system of tumor cells, reduce mitochondrial membrane potential (MMP), activate Caspase, induce lipid peroxidation (LPO) accumulation, cause mitochondrial shrinkage, and downregulate glutathione peroxidase 4 (GPX4), ultimately leading to cancer cell death.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203193","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":"Unconventional coordination modes of carboranyl phosphine-iminophosphorane ligands","authors":"José Luis Rodríguez-Rey, Irene Vázquez-Carballo, Antonio Sousa-Pedrares","doi":"10.1039/d5dt02122g","DOIUrl":"https://doi.org/10.1039/d5dt02122g","url":null,"abstract":"A series of new carboranyl phosphine-iminophosphorane ligands were obtained and characterized. The ligands present a flexible three-atom spacer between (P, N) donor atoms, derived from the diphosphine dppe. The ligands include examples of C-carboranyl derivatives (ligands L1-L3) and B3-carboranyl derivatives (ligands L4 and L5), to compare the different effect of these electron-withdrawing groups. An organic analog was also prepared (ligand L6) for comparison purposes. The analysis of the structures of their dichloride palladium(II) complexes using several techniques, including X-ray diffraction, reveals that the carboranyl group can affect the coordinating ability of the attached nitrogen atom. Thus, although organic phosphine-iminophosphorane ligands always show the (P, N) chelating mode, providing both sites are available, the new carboranyl ligands give rise to a surprising variety of coordination modes: the expected (P, N) chelating mode, the unusual P-terminal mode and the unprecedented (P, N) bridging mode. The comparison of these structures with organic analogues and with the carboranyl ligands derived from the diphosphine dppm indicate that the length of the spacer between the donor atoms is an important variable for the coordination mode of the ligand, once the coordinating strength of the nitrogen atom is reduced by effect of the carborane cage.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"39 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203196","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":"Perylenediimide-based Metal-Organic Frameworks: Structural, Electrochemical and Spectroelectrochemical Characterisation","authors":"Joseph O. Ogar, Edward Stephen Davies, Asia Almuhana, Sarah Griffin, Matthew A. Addicoat, Stephen Argent, Neil R. Champness","doi":"10.1039/d5dt02244d","DOIUrl":"https://doi.org/10.1039/d5dt02244d","url":null,"abstract":"The electrochemical and spectroelectrochemical behaviour of metal-organic frameworks (MOFs) using a perylene diimide (PDI) based ligand is reported. Through suitable functionalisation, a PDI-based ligand is made soluble, allowing successful synthesis of two MOFs in combination with cobalt dicarboxylate paddlewheel secondary building units. Spectroelectrochemical techniques are used to probe the electrochemical and optical behaviour of the MOFs demonstrating that the properties of the perylene diimide are maintained by the MOF, facilitating electrochromic behaviour.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"101 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203195","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 high-capacity and stable rate-performance Li-ion battery anode using hierarchical microcakes in-situ growing with nanoflakes","authors":"Zhen Peng, Ting Zhou, Zicong Yan, Zhongbing Li, Hang Su, Fei Wang, Jinjin Li, Jinyun Liu","doi":"10.1039/d5dt01948f","DOIUrl":"https://doi.org/10.1039/d5dt01948f","url":null,"abstract":"Designing high-performance anode materials is highly required and significant for developing next-generation Li-ion batteries since currently available graphite-based anode can hardly meet the need of advanced battery systems. Here, we develop a Fe2O3 microcake growing with Cu0.75Co2.25O4 nanoflakes, forming a hierarchically micro-nanostructured Fe2O3@Cu0.75Co2.25O4 composite, which exhibits high electrothermal performance as Liion battery anode material. Hierarchical structure effectively prevents the deterioration of cycling performance caused by large volume-change during cycling, while the nanoflakes growing on microcakes facilitate transport of ions and electrons. The results show that the Fe2O3@Cu0.75Co2.25O4 microcakes-based anode displays a high and stable capacity of 1029 mAh g⁻¹ after 100 cycles at 0.2 A g⁻¹, and stable rateperformance is also achievable. Moreover, in-situ X-ray diffraction study indicates reversible phase conversion upon charge-discharge. Our findings provide a promising design of hierarchical microcake structure for developing high-performance energy-storage composites and their secondary batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203198","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 ‘turn-on’ iridium(III) complex probe for visualizing mitochondrial SO2 fluctuation in cancer cells and tumor models","authors":"Si-Yu Chen, Meng-Sen Chen, An-Li Liu, Gao-Nan Li, Fabiao Yu, Zhi-Gang Niu","doi":"10.1039/d5dt01854d","DOIUrl":"https://doi.org/10.1039/d5dt01854d","url":null,"abstract":"Mitochondrial sulfur dioxide (SO2) plays critical biological roles in physiological processes. Notably, abnormal endogenous SO2 levels serve as potential biomarkers for early diagnosis of tumors. Therefore, visual detection of SO2 in cancer cells and tumor models is a subject of significant interest. A ‘turn-on’ iridium(III) complex probe (Ir-CHO) was designed and synthsized, utilizing 2-phenylpyridine (ppy) as the main ligand and 2-(pyridin-2-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (PIP-CHO) as the ancillary ligand, for identifying SO2 in living Hela cells and tumors through bioimaging. The probe exhibits some outstanding properties, including high phosphorescence quantum yield (31.1%), microsecond lifetime (0.61 µs), relatively low detection limit (0.68 μM), rapid response (&lt;1 min), excellent photostability (&gt;60 min), high selectivity and specificity, low cytotoxicity, and mitochondria-targeted ability (PCC=0.805). Based on these properties, the probe was successfully applied to visualize endogenous and exogenous SO2 in living cells and effectively distinguish normal mice and tumor mice with negligible systemic toxicity. All the results suggest that this new probe Ir-CHO could monitor SO2 derivatives in real-time within tumor microenvironment research, highlighting its promising diagnostic potential for future clinical and biomedical applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195502","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":"An acetate bridged centrosymmetric trinuclear Zn(II) cluster: structural insights, biomolecular interactions, sensing and cytotoxic activity.","authors":"Imtiyaz Ahmad Mantoo,Masrat Bashir,Mushtaq Ahmad Nengroo,Shahnawaz Ali Bhat,Imtiyaz Yousuf","doi":"10.1039/d5dt02057c","DOIUrl":"https://doi.org/10.1039/d5dt02057c","url":null,"abstract":"A multifunctional trinuclear zinc cluster with the formula [Zn3L2(μ1,2-OAc)2(μ1,1,2-OAc)2] (C1) was synthesized from a tridentate Schiff base ligand (L1) and thoroughly characterized by various spectral (FTIR, 1H & 13CNMR, UV-vis, and sc-XRD studies) and analytical techniques. The sc-XRD studies of C1 revealed a monoclinic crystal system with a space group of P21/c, wherein three zinc (Zn3) centers are bridged via four acetate ions. The DFT and TDDFT studies were also performed to validate the chemical and electronic structures of the Zn(II) cluster. The HOMO electron density is mainly restricted on the bridging acetate ions and the ligand moiety while the LUMO electron density is distributed throughout the metal complex. We exploited the sensing activity of the Zn(II) cluster using spectral techniques which validated a selective and efficient sensing of Al3+ ions in aqueous medium. Moreover, the catecholase activity of C1 was evaluated and interestingly, our results indicated a ligand-centered radical pathway with a remarkable catalytic activity. We further carried out in vitro biomolecular interactions with ct-DNA using multispectral methods to authenticate the chemotherapeutic potential of C1. Furthermore, the cytotoxicity of C1 was evaluated against HCT116 (colon cancer), MDA-MB-231 (triple-negative breast cancer) and SH-SY5Y (neuroblastoma) cancer cells and toxicity studies were carried out against the normal VERO (kidney) cell line which revealed selective cytotoxicity of C1 against the MDA-MB-231 cancer cells with a remarkably low IC50 value.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"53 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194915","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":"Stability, Structure, Dynamics and Thermal Properties of C-type Aluminiumtrisdihydrogenphosphate","authors":"Sheyi Clement Adediwura, Jan Konrad Wied, Christian Franz Litterscheid, Jörn Schmedt auf der Günne","doi":"10.1039/d5dt02141c","DOIUrl":"https://doi.org/10.1039/d5dt02141c","url":null,"abstract":"Among the fastest hydrogen ion conductors are various hydrogen-rich phosphates, such as phosphoric acid and CsH<small>₂</small>PO<small>₄</small> . This in principle makes Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small> a promising candidate for proton conduction within its hydrogen bonding network, especially in the medium-temperature range. Here, the phase-pure synthesis and structural details of the ferroelectric crystal C-type Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small> are reported, where density functional theory (DFT) calculations were used to study the thermodynamic stability of different Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small>polymorphs. Its ion conductivity as determined by impedance spectroscopy is an order of magnitude higher than previously reported. The thermal stability and the decomposition route of Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small> were studied using XRD, thermal analysis, and solid-state NMR, yielding results different from those previously observed in various mixtures containing Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small>. Heating produces an amorphous intermediate phase which converts into phase-pure monoclinic Al<small>₂</small>(P<small>₆</small>O<small>₁₈</small>), which at even higher temperatures converts into the cubic phase Al<small>₄</small>(P<small>₄</small>O<small>₁₂</small>)<small>₃</small> and little AlPO<small>₄</small> . Rietveld refinements of C-type Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small> and Al<small>₄</small>(P<small>₄</small>O<small>₁₂</small>)<small>₃</small> are provided. The results show that while the proton ion conductivity of C-type Al(H<small>₂</small>PO<small>₄</small>)<small>₃</small> is hampered by the strong hydrogen-bonds, the structure features a Curie temperature significantly higher than room-temperature.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"72 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195394","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":"Enhancement in the performance of Nb14W3O44 high power anodes through P doping in the tetrahedral sites","authors":"Alex James Green, James W Annis, Dominic John Gardner, Aron Spiller, Phoebe K Allan, Peter R. Slater","doi":"10.1039/d5dt02060c","DOIUrl":"https://doi.org/10.1039/d5dt02060c","url":null,"abstract":"Niobium-based anodes are emerging as promising candidates for high-power lithium-ion batteries due to their high theoretical capacities, robust safety at high current densities, and excellent long-term cycling stability. In this respect Nb14W3O44 (NWO) has been attracting significant interest, and in this work, we investigate for the first time phosphorous-doping into this phase. Structural characterisation confirmed the substitution of phosphorous into the tetrahedral sites of the NWO framework, with a resulting contraction in the unit cell dimensions. Electrochemical testing demonstrated superior capacities for the P-doped materials, attributed to the replacement of W in the tetrahedral sites by non-reducible P, with a corresponding increase in W content in the octahedral sites. The P doped samples also showed excellent rate capability, with x = 0.5 and x = 1 retaining high capacities of 180(5) and 190(10) mA h g-1 at 2 A g-1, respectively and 163(15) and 166(12) mA h g-1 at 4 A g-1 respectively, which could be additionally related to the P doping reducing particle size, which shortens lithium-ion diffusion paths. These results suggest further studies are warranted on the effect of such site-selective doping on the structure and morphology control, and the resulting influence on the electrochemical properties, in other Wadsley Roth niobate anodes with tetrahedral sites.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"99 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195395","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 Ru doped Fe/nickel foam with efficient oxygen evolution reaction using a simple one-step electrodeposition technique","authors":"Ruiling Hu, Lingping Jiang, Yaxin Wang, Min Zhao, Congrong Wang, Miao Zhang, Lei Yang, Wanbing Gong, Jianguo Lv","doi":"10.1039/d5dt02126j","DOIUrl":"https://doi.org/10.1039/d5dt02126j","url":null,"abstract":"Developing OER electrocatalyst with high efficiency and long-term stability using a simple method is of great significance for water splitting. However, the lack of easily accessible active sites and the degradation of durability caused by reconstruction during the reaction process remain challenges. Herein, we successfully prepared Ru doped Fe on nickel foam (NF) using a facile electrodeposition method. Benefiting from the synergistic effect of porous structure and more accessible active sites, Ru-0.01-Fe/NF-2.5 posses the small OER overpotential of 134 and 168 mV at current densities of 10 and 100 mA cm-2, respectively. More significantly, the electrolytic cell assembled with Ru-0.01-Fe/NF-2.5 and Pt/C as anodes and cathodes for overall water splitting only requires a low voltage of 1.46 V to achieve the current density of 10 mA cm-2. In addition, the electrolytic cell maintained robust stability even after continuous operation of 48 hours at a high current density of approximately 100 mA cm-2. This work may open an avenue to construct OER effective electrocatalyst via facile method, and promote their applications in industrial water electrolysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195503","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}