Dalton Transactions最新文献

{"title":"Iron oxide nanospheres: dual functionality as MRI contrast agents and magnetic fluid hyperthermia therapeutics†","authors":"Margherita Porru, Francesca Brero, Carlos Dìaz-Ufano, Manuel Mariani, Francesco Orsini, Paolo Arosio, Marìa del Puerto Morales and Alessandro Lascialfari","doi":"10.1039/D5DT00609K","DOIUrl":"10.1039/D5DT00609K","url":null,"abstract":"<p >Magnetic nanoparticles offer the possibility of combining diagnostic and therapeutic purposes within a single nano-object. In this work, we explore two distinct sets of iron oxide-based nanospheres for their application as contrast agents in magnetic resonance imaging and as heating mediators in magnetic fluid hyperthermia. The nanoparticles were produced with the <em>green</em> microwave polyol-assisted method. The nanoparticles in the first set have a mean core diameter of 11 nm and are coated with polyacrylic acid (PAA), carboxymethyl-dextran (CM-D), or dimercaptosuccinic acid (DMSA). The second set has nanoparticles of a mean diameter of 14 nm, which are coated with PAA or CM-D. The longitudinal and transverse <small>¹</small>H-NMR nuclear relaxivities (<em>r</em><small>_1,2</small>) exhibit a field behavior that depends on the particle core size and on the coating. It is shown that the combination of size and coating is relevant to optimize the relaxometric efficiency, with the PAA coating being able to double the <em>r</em><small>₂</small> efficiency for the smallest size. The heating release was evaluated under various combinations of external alternating magnetic fields, with frequency values ranging from 102.2 kHz to 971.2 kHz and amplitude values ranging from 7 mT to 40 mT. The results indicate that the heating efficiency is independent of the coating for both the 11 and 14 nm particles, while it is significantly higher for the samples of largest size. We conclude that the combination of size and coating (<em>i.e.</em>, surface modifications) of the magnetic nanoparticles can play a crucial role in the relaxometric and heating properties of magnetic nanoparticles with core size of &lt;15 nm.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 22","pages":" 9057-9068"},"PeriodicalIF":3.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt00609k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065931","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 Diversity of Nucleotide Coordination Polymers of Cytidine Mono-, Di-, and Tri-Phosphates and Their Selective Recognition of Tryptophan and Tyrosine","authors":"Yaqoot khan, Yunyun Du, Li Yan, Niu Zhang, Menglei Zhang, Hongwei Ma, Hui Li","doi":"10.1039/d5dt00786k","DOIUrl":"https://doi.org/10.1039/d5dt00786k","url":null,"abstract":"Understanding the coordination geometry of nucleotide mono-, di-, and triphosphates is pivotal for unraveling the intricate relationships between molecular structure and biological function, particularly in metal–ligand interactions and their role in biomolecular recognition. This study investigates the structure of nucleotide-metal polymers and their selective interactions with amino acids, specifically Tryptophan (Trp) and Tyrosine (Tyr). We synthesized and comprehensively analyzed five coordination polymers of cytidine-nucleotides: cytidine monophosphate (CMP), deoxycytidine monophosphate (dCMP), cytidine diphosphate (CDP), and cytidine triphosphate (CTP): {[Cu(CMP)(bpa)(H₂O)₃](CMP)·3H₂O}n (1), {[Cu₂(dCMP)(4,4′-bipy)₂(H₂O)₂]·4H₂O}n (2), {[Cu₂(CDP)₂(azpy)(H₂O)]·3H₂O}n (3), {[Cd₂(CDP)₂(bpa)₂(H₂O)₂]·8H₂O}n (4), and {[Cu(CTP)(2,2′-bipy)]·2H₂O}n (5), where (3), (4) and (5) mark the first report of CDP and CTP coordination complexes. Single crystal X-ray diffraction unveiled the structure of the polymers to be one-dimensional (1, 5) or two-dimensional (2, 3, 4). Circular dichroism (CD) spectroscopy in both the solid and solution states elucidates the chirality-driven assembly in these nucleotide-metal polymers. The selective interactions of coordination polymers with Tryptophan (Trp) and Tyrosine (Tyr) were studied using spectroscopic titrations. Experimental and computational analyses reveal distinct interactions between all five coordination polymers and the amino acids, highlighting their biosensing potential. Binding affinity variations across the polymers offer insights into nucleotide-metal coordination chemistry and suggest applications in molecular recognition and functional materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066322","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":"Emergence of a bismuth-based metal-organic framework as an X-ray scintillator","authors":"Peng Lin, junpu yang, Weinan Sun, Xiaoyuan Zhou, Fangbo Zhao, Jian Lin","doi":"10.1039/d5dt00965k","DOIUrl":"https://doi.org/10.1039/d5dt00965k","url":null,"abstract":"We report the first study of a bismuth-based metal-organic framework as a scintillator for X-ray detection and imaging. The newly synthesized Bi-TCPE exhibits strong photoluminescence and efficient X-ray-induced radioluminescence, along with remarkable stability. Its integration into a flexible polymer matrix enables X-ray imaging, highlighting the great promise of Bi-MOFs as a new class of low-toxicity scintillators.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"125 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066326","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":"SIMDAVIS 1.2: Phosphonates are outstanding SIM ligands. Crown ethers are not.","authors":"Walter Cañón-Mancisidor, Christopher Gonzalez Ponce, Lorena E. Rosaleny, Alejandro Gaita-Ariño","doi":"10.1039/d5dt00417a","DOIUrl":"https://doi.org/10.1039/d5dt00417a","url":null,"abstract":"This study presents SIMDAVIS 1.2, an updated dataset and analysis tool for lanthanide-based single-ion magnets (Ln-SIMs), focusing on the role of various ligands in influencing their magnetic properties. The revised dataset, accessible via a user-friendly online dashboard, encompasses over 10,000 data points on chemical and physical properties derived from more than 400 publications. Notably, the study redefines ligand classifications, introducing phosphonate-based ligands as a distinct family and highlighting their superior performance as SIM ligands compared to less effective alternatives such as crown ethers. Phosphonates exhibit promising pentagonal bipyramidal geometries that enhance magnetic stability by minimizing low-energy vibrational interactions. Comparative analysis reveals that while phosphonates may have moderate U<small>_eff</small> values compared to other leading ligands, their magnetic memory and hysteresis properties are comparable to those of bis-phthalocyaninato or metallocene sandwiches. This work emphasizes the importance of rational ligand selection and frugal data-driven approaches in the design of effective Ln-SIMs, contributing valuable insights into the optimization of single-ion magnet design strategies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066934","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":"Thermally labile monoalkyl phosphates and their alkali metal derivatives: synthesis and solid-state supramolecular aggregation","authors":"Anuj Kumar, Ramaswamy Murugavel","doi":"10.1039/d5dt00255a","DOIUrl":"https://doi.org/10.1039/d5dt00255a","url":null,"abstract":"New organic-soluble monoalkyl phosphate esters [(RO)P(O)(OH)2] have been synthesized by esterification of phosphoric acid with the corresponding aliphatic alcohols in the presence of acetic anhydride. The products were initially isolated as the cyclohexylamine salts, viz. [CyNH3]2[(CF3CH2O)PO3]H2O (1) and [CyNH3]2[((CH3)3CCH2O)PO3]H2OMeOH (3). Neutralization of these cyclohexylamine salts by a suitable ion exchange resin gave the corresponding phosphates esters [(RO)P(O)(OH)2] (R = CF3CH2 (2); (CH3)3CCH2 (4). Reactivity of the trifluoroethyl phosphates 1 and 2 towards lithium and sodium ions have been explored and new alkali metal phosphate complexes [(CF3CH2PO4HLi)3]n (5), [(CF3CH2PO4HNa)2]n (6) and [CF3CH2OPO3(Na0.5)2)(CyNH3).(H2O)6]n (7) have been isolated. Compounds 17 were characterized by different spectroscopic and analytical methods and their molecular structures were established by single-crystal X-ray diffraction studies. These alkyl phosphates and their complexes undergo diverse secondary interactions due to the presence of POH and P=O groups to result in the formation of layered structures. The new alkali metal phosphates have been shown to be efficient single-source precursors to produce useful ceramic phosphates such as LiPO3, NaPO3, and MCoPO4 (M = Li and Na), through facile decomposition involving only gaseous by-products. This chemistry is expandable to generate other transition metal phosphates incorporating alkali metal ions such as LiFePO¬4 etc.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"122 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980126","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":"Unusually Short Au(III)···Au(III) Aurophilic Contacts between Anions. Necessity of Counterions","authors":"Steve Scheiner, Mariusz Michalczyk, Wiktor Zierkiewicz","doi":"10.1039/d5dt00879d","DOIUrl":"https://doi.org/10.1039/d5dt00879d","url":null,"abstract":"Certain crystals contain unusually short contacts between Au(III) species, sometimes interpreted as unsupported aurophilic interactions. Calculations at various levels of theory, including CCSD(T)/CBS, demonstrate the potentials between anions containing these Au(III) centers are purely repulsive, despite the presence of noncovalent bonding between the Au centers. The occurrence of these anion∙∙∙anion dimers in the crystal structure are dependent on the presence of counterions. On the other hand, rearranging the orientations of the anions relative to one another can yield metastable minima, albeit with energies much higher than a pair of fully dissociated species.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980058","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":"Tris(pentafluoroethyl)difluorophosphorane for Fluoride Abstraction and Ligand Exchange Reactions of N-Heterocyclic Carbene and Cyclic Alkyl(amino)carbene Copper(I) Fluorides","authors":"Melanie Riethmann, Steffen A. Föhrenbacher, Christian Luz, Nikolai Ignat'ev, Maik Finze, Udo Radius","doi":"10.1039/d5dt00904a","DOIUrl":"https://doi.org/10.1039/d5dt00904a","url":null,"abstract":"The synthesis and structural characterization of a variety N-heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated cationic copper(I) complexes, featuring the weakly coordinating tris(pentafluoroethyl)-trifluorophosphate counteranion (FAP− anion, [(C2F5)3PF3]−). Starting with the complex [(IDipp)Cu(C6Me6)]+FAP− (IIa) reported previously,1 a series of mononuclear complexes [(IDipp)Cu(LB)]+FAP− ((IDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene) was obtained via ligand exchange of C6Me6 with neutral two valence electron (2 VE) donor molecules (LB = NH3, 1; C6H12N2 = DABCO, 2; C7H10N2 = DMAP, 3; C4H4N2 = pyrazine, 4; C13H9N = acridine, 5; η1-O=C13H9N = acridone, 6; C4H10S = SEt2, 7; C4H8S = THT, 8; PCy3, 9), alongside the dinuclear species [{(IDipp)Cu}2(C2H3N3)2]2+2FAP− (10) with 1,2,4-triazole. In a parallel strategy, [(cAACMe)Cu(C6Me6)]+FAP− (IIb) was employed as precursor for Cu(I) complex formation, leading to [(cAACMe)Cu(LB)]+FAP− (LB = C7H10N2, 13; C4H10S, 14) and the dinuclear complexes [{(cAACMe)Cu}2{C6H12N2}]2+2FAP− (11) and [{(cAACMe)Cu}2{C4H4N2}]2+2FAP− (12). Additionally, the reaction of [(carbene)CuF] with (C2F5)3PF2 in the presence of different 2 VE donor ligands induced fluoride replacemant with a 2 VE donor ligand (LB). This strategy facilitated the isolation of a broad range of complexes of the type [(carbene)Cu(LB)]+FAP−, including [(IDipp)Cu(LB)]+FAP− (LB = (N≡CMe)2, 16; N≡CPh, 17; NH2Ph, 18; NHPh2, 21; NC5H5, 22; NC5H3F2, 24; NC5H2F3, 25; η1-O=CPh2, 27), [(SIDipp)Cu(NH2Ph)]+FAP− (19) (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidin-2-ylidene) and [(cAACMe)Cu(LB)]+FAP− (cAACMe = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; LB = N≡CMe, 15; NH2Ph, 20; NC5H5, 23; THF, 28). Additionally, the dinuclear complex [{(IDipp)Cu(μ-ONC5H5)}2]2+2FAP− (26) was obtained upon reaction with pyridine-N-oxide. In all cases the carbene ligand stayed intact and the formation of Lewis acid/base pairs of the 2VE ligand and (C2F5)3PF2 was never observed. As a result, mixtures of [(carbene)CuF] and (C2F5)3PF2 may serve as synthon for [(carbene)Cu]+, as demonstrated in this work.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980056","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":"Enhancing Electrocatalytic Water Oxidation: Ligand Complementarity in Ternary Cu (II) Complexes","authors":"PRANJAL DAS, Hemrupa Kuilya, Swati Basak, Baisali Hazarika, Joydeep Ray, Debajit Sarma, Diganta Choudhury, Apurba Kalita","doi":"10.1039/d5dt00790a","DOIUrl":"https://doi.org/10.1039/d5dt00790a","url":null,"abstract":"Electrocatalytic water oxidation activity of two mononuclear ternary copper (II) complexes, 1, [Cu(bipy)(HL<small>₁</small>)](ClO<small>₄</small>)<small>₂</small>, [bipy = 2,2/<small></small>-bipyridine, HL1<small></small> = N<small>¹</small>-(2-aminoethyl)ethane-1,2-diamine] and <strong>2</strong>, [Cu(phen)(HL<small>₁</small>)](ClO<small>₄</small>)<small>₂</small>, [phen = 1, 10-phenanthroline], have been investigated. Complexes <strong>1</strong> and <strong>2</strong> exhibit turnover frequencies (TOF) of 483 s<small>^-1</small> and 445 s<small>^-1</small> at overpotentials of approximately 453 mV and 493 mV, respectively, in neutral phosphate buffer. These ternary complexes demonstrate superior catalytic performance compared to their binary counterparts. In these ternary complexes, both ligands act complementarily to enhance stability and redox activity, which are crucial for catalytic performance of the metal complexes. Electrochemical investigations further reveal that structural flexibility of the aliphatic amine ligand moiety influences the overall catalytic efficiency of the ternary metal complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"143 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980055","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":"Au-Involving Chalcogen Bond in 4-(2-Chalcophenyl)-1,2,3-triazolylidene Au(I) Complexes: Synthesis, Characterization and Photophysical Properties","authors":"Jingli Zhang, Xingyu Xu, Xiaoyu Yan","doi":"10.1039/d4dt03508a","DOIUrl":"https://doi.org/10.1039/d4dt03508a","url":null,"abstract":"Noncovalent interactions, particularly ChBs, have gained prominence in modern chemistry due to their tunability and directionality. We present a pioneering investigation of d10 metal-involving chalcogen bond in triazolylidene Au(I) complexes. The crystal structures reveal the occurrence of intramolecular ChBs between Au(I) and chalcophene substituents positioned on the wingtip of triazolylidene ligands. The strength of these ChB interactions can be effectively modulated by altering the chalcophene moieties and ancillary ligands associated with Au(I). The neutral LAu(I)X complexes exhibit remarkable phosphorescence, with PLQY reaching up to 70% in solid state, which are attributed to the rigid structure with intramolecular ChB between Au and chalcogen atom. Moreover, density functional theory (DFT) calculations were performed to obtain insights into the natuer of ChB interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980057","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":"Radical-Friedel-Crafts Benzylation of Arenes over the Metallic-Basic Bifunctional MoO2 Surface","authors":"Zhuo Li, Kaiyi Su, ting li, Jinlan Cheng, Bo Jiang, Tingwei Zhang, Chaofeng Zhang","doi":"10.1039/d5dt00631g","DOIUrl":"https://doi.org/10.1039/d5dt00631g","url":null,"abstract":"Selective ether bond activation is essential in organic synthesis and natural polymer depolymerization. Herein, we reported that the MoO2 with negligible acidity but metallic-basic bifunctional characterization could efficiently catalyze the benzylation of arenes with benzyl ethers as the benzylation reagent via a Radical-Friedel-Crafts mechanism. Combined with the catalyst characterizations, control experiment, thermomechanical analysis, intermediates capture, and density functional theory (DFT) calculations, the multiple Mo sites over the MoO2 surface can achieve the oxygen-centered group firstly transfer from the adsorbed dibenzyl ether (DBE*) with the homolytic cleavage of Bn–OBn ether bonds, which was promoted by the adjacent group auxiliary activation of the benzyl aromatic ring adsorbed on the MoO2 surface. The generated benzyl radical (Bn•) then attacks the aromatic ring of the arene substrates, and the first-exfoliated oxygen-centered group (BnO*) and its potential decomposition fragment of oxygen atom species Mo=O* with oxidative properties can abstract the H atom from the above addition-intermediate to restore the aromaticity and achieve the benzylation. The remaining alcohol (BnOH) can also participate in the benzylation mediated by the MoO2. This study could provide some inspiration about the C–O bond activation and ether utilization mediated by the Mo-based catalyst.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980054","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}