Zhujun Sheng, Yuanzheng Liu, Li Xu, Xin Yao, Ju Chen, Yunjun Liu, Xiu-Zhen Wang
{"title":"Synthesis, characterization and induction of ferroptosis of iridium(III) complexes against melanoma B16 cells","authors":"Zhujun Sheng, Yuanzheng Liu, Li Xu, Xin Yao, Ju Chen, Yunjun Liu, Xiu-Zhen Wang","doi":"10.1039/d5dt00899a","DOIUrl":"https://doi.org/10.1039/d5dt00899a","url":null,"abstract":"The synthesis of ligand, 2-(2-methyl-4-hydroxyl)phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (MHIP), and corresponding new iridium(III) complexes: [Ir(ppy)2(MHIP)]PF6 (ppy = 2-phenylpyridine, 9a), [Ir(bzq)2(MHIP)]PF6 (bzq = benzo[h]quinolone, 9b) and [Ir(piq)2(MHIP)]PF6 (piq = 1-phenylisoquinoline, 9c) were reported. The antiproliferative activity of compounds 9a-9c on cancer HepG2, B16, A549 cells, normal LO2 cells were tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, it was found that the three complexes showed moderate cytotoxicity on A549 and B16 cells. However, after further irradiation, the cytotoxicity was greatly enhanced, especially, 9a, 9b and 9c display significant cytotoxicity toward B16 cells with a low IC50 value of 3.1 ± 0.3 µM for 9a, 4.9 ± 0.8 µM for 9b, and 0.4 ± 0.1 µM for 9c, respectively. The effects of 9a-9c on the invasive ability of B16 cells were explored by colony formation and scratch experiments, the results demonstrate that the complexes can efficiently block the cell proliferation and migration. The co-localization assay found that 9a-9c accumulate in the mitochondria and lead to the apoptosis of B16 cells by decreasing the mitochondrial membrane potential, altering the structure of microtubule proteins, damaging the structure of the cellular DNA, and changing the expression of related proteins. The decrease of glutathione (GSH) concentration, the increase of malondialdehyde (MDA), the downregulation of GPX4, and C11-BODIPY staining results confirmed that 9a, 9b and 9c led to ferroptosis. In addition, we explored the relevant signaling pathways through RNA sequencing assay and speculated on possible anticancer mechanisms. Together, these results indicate that the synthesized new iridium(III) complexes 9a-9c can induce cell death via a ROS-mediated mitochondrial dysfunction apoptosis and ferroptosis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088191","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":"Impact of ether coordination on the solid-state luminescence of a lithium β-diketiminate complex.","authors":"Shunichiro Ito,Kazuo Tanaka,Yoshiki Chujo","doi":"10.1039/d5dt00954e","DOIUrl":"https://doi.org/10.1039/d5dt00954e","url":null,"abstract":"A solid-state luminescent lithium β-diketiminate complex was synthesized by the reaction of the corresponding proligand and n-butyllithium in hexane. The complex showed a low-coordinated structure in the solution and crystalline states. On the other hand, the lithium complex reacted with diethyl ether, tetrahydrofuran, and 1,4-dioxane to form three-coordinated complexes, which showed lower emission efficiency. Remarkably, the photoluminescence of the crystal of the low-coordinate species was quenched by the treatment with the diethyl ether vapor. NMR spectroscopy and X-ray diffraction analyses revealed that diethyl ether reacts with the complex to afford the three-coordinated ether adduct even in the crystalline state. To the best of our knowledge, this is the first report on the luminescence switching in crystalline materials based on the modification of the coordination number on a lithium atom.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087699","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}
Sheng-Ze Zhao, Liwen Chen, Hai Zhu, Hao-Zhe Zhang, Chang Liu, Chun-Yan Qin, Hai-Ying Wang, Yong-Hua Li, Shi Wang
{"title":"Halogen Bonds-enhanced Spin Dynamics: Investigating Co-crystallization Effects on Spin Crossover in Mononuclear Mn(III) Schiff-base Complexes","authors":"Sheng-Ze Zhao, Liwen Chen, Hai Zhu, Hao-Zhe Zhang, Chang Liu, Chun-Yan Qin, Hai-Ying Wang, Yong-Hua Li, Shi Wang","doi":"10.1039/d5dt00841g","DOIUrl":"https://doi.org/10.1039/d5dt00841g","url":null,"abstract":"We present co-crystallization with 1,3,5-trifluoro-2,4,6-triiodobenzene (TFTIB) as an approach to tuning spin crossover (SCO) properties of mononuclear Mn(III) Schiff-base complexes. The isostructural complexes [Mn(naphth-sal-N-1,5,8,12)]Y (Y= Br (1) and Y=I (2) and (naphth-sal-N-1,5,8,12)2− is a big conjugated hexadentate Schiff-base ligand) share similar magnetic behaviors and among them complex 2 shows a gradual SCO with transition temperature T1/2 ~ 380 K. Complexes [Mn(naphth-sal-N-1,5,8,12)]∙TFTIB∙Y (Y= Br (3) and Y=I (4)) are synthesized by the co-crystallization of their parent complexes 1 and 2 with the TFTIB and they both exhibit more gradual SCO with T1/2 rising to over 400 K. For comparison, complex [Mn(5-F-sal-N-1,5,8,12)]∙2TFTIB∙Br∙CH3CN (5) was also synthesized, which maintains a high spin (HS) state over the measured temperature range. An anion-TFTIB network connected by halogen-halogen bonds has a significant influence on cation-anion crystal packing and finally the cooperative effects of the SCO complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"10 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067051","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":"Adaptive hydrogen-bonding strategy driven 0D manganese-based metal halides with multifunctional fluorescent applications.","authors":"Jiamin Liu,Yuntao Ruan,Qiaoqi Qin,Yong Shen,Zhengliang Wang,Daibin Kuang,Long Jiang","doi":"10.1039/d5dt00491h","DOIUrl":"https://doi.org/10.1039/d5dt00491h","url":null,"abstract":"Herein, we designed organic cations with multiple donor and acceptor sites of hydrogen bonds and reported reversible luminescence modulation in 0D manganese-based metal halides via water-driven in situ structural transformations with the above adaptive hydrogen-bonding cation. The non-fluorescent-to-fluorescent transition at human body temperature highlights their high sensitivity and environmental adaptability as promising candidates for advanced fluorescence-based sensing and anti-counterfeiting applications. Besides, the high photoluminescence quantum yield and great stability of fluorescent (BBD)MnBr4 provide a way to explore OIHMHs pumped by green light for white LEDs.","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":"144065932","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":"Dimensionality-driven photoluminescence enhancement in Cl/Br mixed-halide organic–inorganic hybrid cadmium halides","authors":"Boyoung Kim, Kang Min Ok","doi":"10.1039/d5dt00908a","DOIUrl":"https://doi.org/10.1039/d5dt00908a","url":null,"abstract":"In this study, we report the successful synthesis of four organic–inorganic hybrid materials by systematically varying the Cl/Br halide ratio in a system comprising 4-(2-aminoethyl)pyridine organic cations and cadmium halides. An increase in Cl content induces a structural transition from zero-dimensional to two-dimensional (2D) frameworks, with the 2D phase featuring a unique layered architecture composed of corner-, edge-, and face-sharing Cd-halide octahedra. All compounds exhibit broadband blue photoluminescence, and a clear correlation is observed between halide mixing, increased structural distortion, and enhanced photoluminescence quantum yield (PLQY). Notably, the PLQY increases significantly from 6% to 36% in the 2D mixed halide compound. These findings underscore the effectiveness of halide composition modulation in tuning both structural dimensionality and optical performance, providing valuable insights for the rational design of high-efficiency luminescence materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066323","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 comparative study on nido- and closo-carborane supported zinc-salen catalysts for the ROCOP of epoxides and anhydrides†","authors":"Jin-Bian Xue, Jia-Ni Wang, Ke-Cheng Chen, Qian Cheng, Jia-Ying Zhang and Xu-Qiong Xiao","doi":"10.1039/D5DT00946D","DOIUrl":"10.1039/D5DT00946D","url":null,"abstract":"<p > <em>Nido</em>- and <em>closo</em>-carborane supported Zn–salen complexes (<strong>2–4</strong>) were prepared. The <em>nido</em>-C<small><sub>2</sub></small>B<small><sub>9</sub></small> carborane anion supported Zn–salen complexes are superior to the <em>closo</em>-carborane supported ones in ROCOP of epoxides and anhydrides. These findings show the importance of electronic effects in the backbone of the salen ligands and offer guidance for future catalyst design.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 21","pages":" 8400-8404"},"PeriodicalIF":3.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065933","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}
Andrew J. Stocker, Chloe L. Howells, Nicholas C Fletcher
{"title":"Interpreting solvent effects on complex dihydrogenphosphate binding using amidobenzimidazole functionalised emissive ruthenium diimine complexes","authors":"Andrew J. Stocker, Chloe L. Howells, Nicholas C Fletcher","doi":"10.1039/d5dt00842e","DOIUrl":"https://doi.org/10.1039/d5dt00842e","url":null,"abstract":"The photophysical behaviour of two amidobenzimidazole complexes, [Ru(bpy)<small><sub>2</sub></small>(bbiab)](PF<small><sub>6</sub></small>)<small><sub>2</sub></small> and [Ru(phen)<small><sub>2</sub></small>(bbiab)](PF<small><sub>6</sub></small>)<small><sub>2</sub></small> (where bbiab = 4,4`-bis(N-1H-benzimidazol-2-yl-carboxamidyl)-2,2`-bipyridine) in a variety of solvents suggest that the 3MLCT state is sensitive to the introduction of small aliquots of solvent (dilution) resulting in distinct incremental changes to the absorption spectra, and quenching in emission. This solvent dependency is more pronounced in polar media and is proposed to be a consequence of “dimerization” of these complexes, which is supported by <small><sup>1</sup></small>H-DOSY-NMR spectroscopy and gas phase DFT studies on the free ligands. The pH behaviour of these complexes indicates that protonation of the imidazole results in changing the emissive state from the bpy and phen ligands to bbiab. Significant quenching in both complexes is seen on the introduction of acetate, which 1H-NMR spectroscopy suggests is association with the bbiab imidazole groups. On the introduction of HSO<small><sub>4</sub></small><small><sup>−</sup></small> and H<small><sub>2</sub></small>PO<small><sub>4</sub></small><small><sup>−</sup></small> salts, the photophysical response suggests several distinct interactions are present as anion concentration increases, with both the amide and imidazole groups able to act as hydrogen-bond donors and acceptors. These effects are solvent dependent implying a complex set of equilibria, ranging from protonation of the imidazole in non-protic solvents, dissociation of the complex dimer, a simple one-to-one species, and a combined bis(dihydrogenphosphate)-complex anion, with speciation reliant on complex charge, associated ligand hydrophobicity, and solvent.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"57 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066325","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}
Margherita Porru,Francesca Brero,Carlos Dìaz-Ufano,Manuel Mariani,Francesco Orsini,Paolo Arosio,Marìa Del Puerto Morales,Alessandro Lascialfari
{"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,Alessandro Lascialfari","doi":"10.1039/d5dt00609k","DOIUrl":"https://doi.org/10.1039/d5dt00609k","url":null,"abstract":"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 green 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 1H-NMR nuclear relaxivities (r1,2) 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 r2 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 (i.e., surface modifications) of the magnetic nanoparticles can play a crucial role in the relaxometric and heating properties of magnetic nanoparticles with core size of <15 nm.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yaqoot khan, Yunyun Du, Li Yan, Niu Zhang, Menglei Zhang, Hongwei Ma, Hui Li
{"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}