Dalton Transactions最新文献

{"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}

{"title":"A tetranuclear Pr-W heterometal cluster-imbedded antimotungstate for catalytic synthesis of benzimidazoles","authors":"Zhijian Zheng, Song Jiang, Xue-Jiao Chen, Haoqi Liu, Yufeng Liu, Yayu Dong, Xiao-Peng Sun, Guo-Ping Yang","doi":"10.1039/d5dt00386e","DOIUrl":"https://doi.org/10.1039/d5dt00386e","url":null,"abstract":"A novel organic-inorganic Pr-W heterometal cluster-imbedded antimotungstate, [(CH3)2NH2]4Na20.5{[(OAc)Pr4W6O12(tar)3](SbW9O33)4(H2O)10}Cl0.5ca.40.3H2O (Pr-1), was synthesized via one-step in-situ assembly strategy. Pr-1 features a distinctive tetranuclear Pr-based organic-inorganic hybrid structure stabilized by polycarboxylic acid ligands, which efficiently regulate the hydrolysis of Pr3+ to facilitate the assembly of Pr-W heterometallic clusters. Notably, this structure includes abundant Lewis acid sites from Pr3+, making it highly promising for catalytic applications. Pr-1 has been successfully demonstrated as an environmentally friendly, heterogeneous catalyst in synthesizing benzimidazoles from o-phenylenediamines and benzaldehydes. The high catalytic activity, excellent structural stability, and recyclability over five cycles highlight the potential of Pr-1 as an efficient and sustainable catalyst for N-containing heterocyclic organic synthesis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"121 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945966","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":"GAME OF LIGANDS: TUNING PHOTODYNAMIC ACTIVITY OF P(V) PORPHYRINS IN AQUEOUS MEDIA","authors":"Inessa A. Efimova, Evgeniya A. Safonova, Marina A Polovkova, Egor V. Gorshkov, Tatiana V. Egorova, Roman Akasov, Aslan Yu Tsivadze, Yulia G. Gorbunova","doi":"10.1039/d5dt00808e","DOIUrl":"https://doi.org/10.1039/d5dt00808e","url":null,"abstract":"For developing novel photosensitizers (PS), three series of phosphorus (V) tetra-meso-aryl-substituted porphyrins, bearing varying number of pyridyl groups (0 to 2) and different axial ligands (-OH, -OEt, -OPrOH) were obtained. All complexes exhibit fluorescence in EtOH with moderate quantum yields (0.10-0.15) and singlet oxygen (SO) generation with high quantum yields (0.58-0.87). Photostability, fluorescence, and SO generation quantum yields increase with a reduction of the number of pyridyl groups. Moreover, on the example of P(V) mono-pyridyl-substituted porphyrins, it was demonstrated that the photostability and SO generation depend on the nature of the axial ligands, with an increase observed in the following series: -OH &lt; -OPrOH &lt; -OEt. Interestingly, P(V) porphyrins with axial -OH ligands are subject to intracellular dephosphorylation and accumulation in human carcinoma cell organelles (apparently in lysosomes), whereas complexes with axial -OEt groups remain in the initial state and are diffusely distributed throughout the cytoplasm. Remarkably, P(V) complexes exhibit high photoinduced cytotoxicity against human breast adenocarcinoma MCF-7 and human lung adenocarcinoma A-549 cells, with IC50 values reaching the nanomolar range. Mono-pyridyl-three-phenyl and tetraphenyl- complexes bearing -OEt axial ligands are the most promising photosensitizing agents with the highest light cytotoxicity (IC₅₀ =2.0 and 5.7 M for A-549 and 8.9 and 14 nM for MCF-7 cells correspondingly). The dose-dependent effect has also been demonstrated, confirming a light-induced mechanism of cell death.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"117 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946088","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}