Dalton Transactions最新文献

{"title":"A Chloride-doped Cu18 Nanocluster: Synthesis, Bonding and Nonlinear Optical Property","authors":"Xuekun Gong, Chan Zheng, Dongjie Zuo, Simin Li, Wei-Hui Fang, Hui Shen","doi":"10.1039/d5dt00851d","DOIUrl":"https://doi.org/10.1039/d5dt00851d","url":null,"abstract":"Atomically precise copper nanoclusters have emerged as an essential class of materials that have found applications in a wide range of fields. However, the design and development of copper cluster nanomaterials are still in their embryonic stages, with most of the focus being on those containing hydride atoms. In this report, we present the discovery of copper nanoclusters doped with other non-metallic atoms, which represent a new and promising type of material. A novel chloride-doped Cu18 cluster, with the chemical composition of [ClCu18(PET)16(PPh3)4]+ (PET is 2-phenylethanethiol), was synthesized using a one-pot process. The molecular structure of the cluster, as determined by single-crystal X-ray diffraction analysis, reveals the stabilization of the ClCu6 kernel by a Cu12 cage, which is further passivated by thiolate and phosphine ligands. The cluster exhibits typical optical limiting effects, suggesting that copper nanoclusters doped with non-metallic atoms are a new family of advanced materials in the field of nonlinear optics.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920726","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 Tuning of Nodes and Functional Guests of Polyoxometalate@Metal-Organic Frameworks for Enhanced Photocatalytic Oxidative Coupling","authors":"Zhiqiang Jiang, Qi Xin Zhao, Yang Zeng, Tengfei Gong, Zhenxuan Huang, Zeyu Chen, Jiefeng Shen, Weimin Xuan","doi":"10.1039/d5dt00655d","DOIUrl":"https://doi.org/10.1039/d5dt00655d","url":null,"abstract":"Metal-organic frameworks are versatile platforms for photocatalysis owing to their facile capacity to incorporate active sites within organic linkers, nodes and open channels. However, the dual tuning of both nodes and functional guests for enhanced photocatalytic performance remains largely unexplored. Herein, we report the incorporation of functional polyoxometalate guests, {PM10V2} (M = Mo or W), into isoreticular 2D MOFs that are constructed from anthraquinone-derived ligand and dinuclear nodes of {Cd2X(H2O)4} (X = Br or I), yielding isostructural polyoxometalate@metal-organic frameworks, denoted as POMOF 1–POMOF 3. By systematically varying the node from {Cd2Br(H2O)4} to {Cd2I(H2O)4} and polyoxometalate guest from {PMo10V2} to {PW10V2}, we achieve a structure evolution from POMOF 1 to POMOF 3. Notably, POMOF 1 shows the highest activity towards photocatalytic oxidative coupling of benzylamine and its derivatives due to the synergistic effect of {PMo10V2} and {Cd2Br(H2O)4}, which facilitates the highest photocurrent and an optimal band gap distribution for reactive oxygen species formation and substrate activation. This study demonstrates a promising strategy for designing photocatalytic active materials with enhanced performance via dual regulation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920728","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":"Precisely tailoring Lewis pairs in polyoxotitanium clusters for efficient photocatalytic production of hydrogen peroxide","authors":"Mengke Gao, Shiming Zhang, Yayu Yan, Zehao Qian, Liyang Qin, Xiaoyu Liu, Qing-Rong Ding, Qiao-Hong Li, Xin Wu, Jian Zhang","doi":"10.1039/d5dt00085h","DOIUrl":"https://doi.org/10.1039/d5dt00085h","url":null,"abstract":"Hydrogen peroxide (H₂O₂) is a vital chemical with promising potential as an energy carrier. Photocatalytic H₂O₂ production has emerged as a sustainable and environmentally friendly approach. However, current photocatalysts often exhibit low catalytic efficiency and limited tunability of their electronic structures. Herein, we demonstrate a Lewis pair-dependent strategy for photocatalytic H₂O₂ generation using two N-based polyoxotitanium clusters. Photocatalytic experiments reveal that the Ti₃Co cluster achieves an exceptional H₂O₂ production rate of 1140 μmol g⁻¹ h⁻¹, exceeding that of the Ti₃Mn cluster by more than threefold. Theoretical investigations confirm that functional modifications of the metal-nitrogen Lewis pair in polyoxotitanium clusters induce asymmetric charge distribution and narrow band gap structures. These effects significantly enhance surface charge separation and transfer, leading to improved H₂O₂ yields. This work underscores the potential of atomic-level catalyst design and offers a promising pathway for advancing polyoxotitanium cluster-based photocatalysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"75 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920730","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":"Cadmium sulfide quantum dots functionalized with serine, proline, and aspartic acid homologs to study the influence of ligand size on the induced circular dichroism.","authors":"Milan Balaz, Yoonbin A. Joh, Krisztina Varga","doi":"10.1039/d5dt00778j","DOIUrl":"https://doi.org/10.1039/d5dt00778j","url":null,"abstract":"Chirality, a fundamental property of molecules and materials, underlies numerous critical chemical, biochemical, and optical phenomena. Chiral organic molecules, termed capping ligands, have been shown to induce chirality in intrinsically achiral nanomaterials through electronic and structural interactions, as evidenced by the emergence of a circular dichroic (CD) signal. The sign and intensity of the CD spectra have been demonstrated to reflect both the ligand's absolute configuration and its binding geometry that could be tuned by solvent, temperature, base, countercation, and ligand’s concentration. To gain a deeper understanding of ligand-induced chirality and facilitate the rational design of chiral materials, it is crucial to investigate the interplay between molecules and nanomaterials at the solid-liquid interface. In this study, we investigate the influence of capping ligand size on the induced CD spectra of colloidal cadmium sulfide quantum dots (CdS QDs) by using homologous pairs of amino acids: serine-homoserine, proline-homoproline, and aspartic-glutamic acids. In parallel, we explore the impact of a third functional group (attached to the achiral carbon) and the distance between the anchoring carboxylate group and this third functional group using spectroscopic techniques. Our findings highlight the significant role of ligand molecular structure and footprint (steric demand) on the induced CD signal of semiconductor nanoparticles. This study further emphasizes the importance of circular dichroism spectroscopy in probing surface binding geometry, ligand surface orientation, and ligand-nanocrystal hybridization.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915839","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":"Alkylzinc-Mediated Transmetallation of a Calcium Hydride","authors":"Kyle G. Pearce, Mary F Mahon, Michael Hill","doi":"10.1039/d5dt00958h","DOIUrl":"https://doi.org/10.1039/d5dt00958h","url":null,"abstract":"The dimeric β-diketiminato calcium hydride, [(BDI)CaH]<small>₂</small> (BDI = HC{(Me)CNDipp}<small>₂</small>; Dipp = 2,6-<em>i</em>-Pr<small>₂</small>C<small>₆</small>H<small>₃</small>), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-<small>^t</small>Bu<small>₂</small>C<small>₆</small>H<small>₃</small>)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-<small>^t</small>Bu<small>₂</small>C<small>₆</small>H<small>₃</small>)(μ-Me)Ca(BDI)].","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915842","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":"Water Soluble Palladium Complexes Bearing NNN-Pincer Ligands: Synthesis, DFT Modeling, cT-DNA Interactions and In Vitro Cytotoxicity Studies Against Breast Cancer Cell Lines","authors":"Hafiz Muhammad Rizwan Sarwar, Muhammad Jamshaid, Sara Masood, Gul-e-Saba Chaudhry, Sameen Fatima, Itrat Zahra, Arusa Akhtar, Muhammad Tahir, Ehsan Ullah Mughal, M. Naveed Zafar","doi":"10.1039/d5dt00224a","DOIUrl":"https://doi.org/10.1039/d5dt00224a","url":null,"abstract":"In the pursuit of designing new anticancer pharmaceuticals and enhancing the therapeutic effectiveness of metal-containing compounds, two new Pd(II) pincer complexes, [Pd(o-LMe)Cl](OTf) (5) and [Pd(o-L′Me)Cl](OTf) (6), where o-LMe is (N2Z,N6Z)-N2,N6-bis(1-methylpyridin-2(1H)-ylidene)pyridine-2,6-dicarboxamide and o-L′Me is (N2Z,N6Z)-N2,N6-bis(1,4-dimethylpyridin-2(1H)-ylidene)pyridine-2,6-dicarboxamide commonly known as pyridylidene amide (PYA) ligands, were successfully synthesized and subjected to characterization through various spectroscopic methodologies. The PYA ligands were generated from proligands, o-H2LMe(OTf)2 (3) and o-H2L′Me(OTf)2 (4) during the complexation reaction. The precursors, 1 (o-H2L) and 2 (o-H2L′), were synthesized by treatment of dipicolinic acid with 2-aminopicoline and 2-amino-4-methylpicoline, respectively, in the presence of triphenyl phosphite followed by methylation to obtain o-H2LMe(OTf)2 (3) and o-H2L′Me(OTf)2 (4). The molecular structure of palladium complex (5)has been thoroughly analyzed through the SC-XRD, revealing a distorted square planar configuration encompassing two five-membered metallacyclic rings. The DFT approach meticulously investigated the electronic features, molecular electrostatic potential, and frontier molecular orbitals of the complexes. The nature of the compound’s interaction with cT-DNA and the implications of pincer-PYA coordination on the binding affinity of Pd(II) complexes were probed through UV-visible spectrophotometry and viscometry. The results elucidated the intercalative mode of interaction alongside elevated binding parameters for 5 (105 dm3/mol) and 6 (104 dm3/mol). Molecular docking of complex 5 was performed, which exhibited a strong interaction with DNA and supported the experimental findings. The in vitro cytotoxic effects of the samples were systematically assessed by MTT protocol on the breast cancer (MCF-7 and T47D) and normal (Vero) cell lines. According to the determined IC50 values, Pd(II) complexes demonstrated a prominent influence in augmenting cytotoxicity. The cytotoxicity values associated with these compounds follow a hierarchy of 5 &gt; cisplatin &gt; 6 &gt; 4 &gt; 3 within neoplastic cells. The apoptotic effects of 5 and 6 on the MCF-7 cancer cell line were examined to elucidate the mechanistic pathway responsible for its maximal cytotoxic efficacy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915846","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":"Recent developments in atomically precise metal nanocluster-based photocatalysts for hydrogen production.","authors":"Rugma T P,Michael N Pillay,C W Liu","doi":"10.1039/d5dt00283d","DOIUrl":"https://doi.org/10.1039/d5dt00283d","url":null,"abstract":"Photocatalytic hydrogen production offers a sustainable approach for utilising light energy, providing a promising solution to global energy challenges. The efficiency of this process relies on developing photocatalysts with broad light responsiveness and effective charge carrier separation capabilities. Atomically precise metal nanoclusters (NCs) have emerged as a highly favourable class of materials for this role due to their unique atomic arrangements, ultrasmall size, quantum confinement effects, and plenty of surface-active sites. These exceptional properties endow NCs with semiconductor-like behaviour, allowing for the generation of electrons and holes under light excitation, thus driving the hydrogen production reaction. Moreover, their robust light-absorption properties across the UV to near-IR spectrum, coupled with tuneable optical properties controlled by their composition and structure, promise NCs as next-generation photocatalysts. This review explores recent developments in the application of NCs for photocatalytic hydrogen production, emphasising strategies to enhance charge carrier separation and transfer efficiency, as well as photostability. The discussion also highlights the challenges and future opportunities in using NCs for efficient hydrogen production.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915169","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":"Reactivity of a dithorium oxo complex from adventitious water†","authors":"Pritam Mahawar, Steven P. Kelley and Justin R. Walensky","doi":"10.1039/D5DT00855G","DOIUrl":"10.1039/D5DT00855G","url":null,"abstract":"<p >The presence of adventitious water in the treatment of [ThCl<small>₄</small>(DME)<small>₂</small>] with two equivalents of [K(C<small>₅</small>Me<small>₅</small>)] results in the formation of the title bridging oxo complex, [{(C<small>₅</small>Me<small>₅</small>)<small>₂</small>ThCl}<small>₂</small>(μ-O)] (<strong>1</strong>). This complex can also be formed from the reaction of [(C<small>₅</small>Me<small>₅</small>)<small>₂</small>ThCl<small>₂</small>] with one equivalent of degassed water. The reactivity of the oxo complex was probed with Me<small>₃</small>SiCl and AlCl<small>₃</small>, resulting in the quantitative formation of [(C<small>₅</small>Me<small>₅</small>)<small>₂</small>ThCl<small>₂</small>]. Treatment of [{(C<small>₅</small>Me<small>₅</small>)<small>₂</small>ThCl}<small>₂</small>(μ-O)] with two equivalents of MeMgCl leads to [{(C<small>₅</small>Me<small>₅</small>)<small>₂</small>ThMe}<small>₂</small>(μ-O)] (<strong>2</strong>) which can be further treated with PhN(H)N(H)Ph, yielding [{(C<small>₅</small>Me<small>₅</small>)<small>₂</small>Th(PhNN(H)Ph)}<small>₂</small>(μ-O)] (<strong>3</strong>). Each complex has been characterized by spectroscopic and structural methods.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 21","pages":" 8706-8711"},"PeriodicalIF":3.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt00855g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural Insights and In Vitro and In Vivo Anticancer Evaluation of Dithiocarbamate-Based Metal Complexes against Murine Lymphoma","authors":"Anupam Singh, Riya Patel, Samrat Daripa, Manoj Kumar Bharty, R. J. Butcher, Sumit Kumar Hira, Lal Bahadur Prasad","doi":"10.1039/d5dt00666j","DOIUrl":"https://doi.org/10.1039/d5dt00666j","url":null,"abstract":"Metal-based chemotherapeutics have gained attention due to their ability to interfere with cellular functions. Dithiocarbamate ligands, known for their strong metal-binding properties, have been explored for their potential in anticancer applications. This study aims to synthesize and characterize dithiocarbamate-based Ni(II), Cu(II), and Zn(II) complexes and evaluate their anticancer activity against Dalton’s lymphoma (DL) cells. Three dithiocarbamate ligands (1-3) and their corresponding Ni(II), Cu(II), and Zn(II) complexes (1a-c, 2a-c, and 3a-c) were synthesized and characterized using FT-IR, NMR, UV-Vis, mass spectrometry, and single-crystal X-ray diffraction (SC-XRD). TGA analysis of complexes confirms their thermal stability up to 150 °C and formation of metal sulfides at elevated temperatures. The in vitro antiproliferative activities of these compounds were assessed using the MTT assay. Apoptosis induction was analyzed via Annexin V-FITC/PI staining and flow cytometry. In vivo studies were conducted on a murine DL tumor model to evaluate therapeutic efficacy and biosafety. SC-XRD confirmed square planar geometries for Ni(II) and Cu(II) complexes, whereas Zn(II) complexes exhibited tetrahedral geometry. Metal complexes 1c, 2b, and 3c displayed the most potent antiproliferative activity, with 1c exhibiting the lowest IC50 (7.1 μM). Apoptosis analysis indicated that 1c induced 64% apoptosis in DL cells. In vivo studies demonstrated that 1c significantly reduced tumor growth and prolonged survival, with minimal toxicity. The synthesized dithiocarbamate-metal complexes exhibit promising anticancer properties, particularly 1c, which demonstrated superior efficacy in both in vitro and in vivo models. These findings highlight the potential of metal-based dithiocarbamates as novel anticancer agents warranting further preclinical studies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915843","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":"Catalytic Regioselective 3,4-Difunctionalization of 3-Iodo-o-Carborane via Pd Migration","authors":"Xianren Jiang, Chang-Hua Ding, Zaozao Qiu, Zuowei Xie","doi":"10.1039/d5dt00981b","DOIUrl":"https://doi.org/10.1039/d5dt00981b","url":null,"abstract":"A Pd-catalyzed one-pot regioselective difunctionalization of 3-iodo-o-carborane has been achieved for the synthesis of a wide variety of 3-alkyl-4-Nu-o-carboranes (Nu = aryl, alkyl, amino, or thio groups) in moderate to excellent yields. This protocol combines the sequential activation of cage B(3)–I and B(4)–H bonds via Pd 1,4-migration.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"48 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920784","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}