Huilin Huang, Qiong Yang, Kun Yao, Wen-Chao Geng, Xu Jing
{"title":"Visible-light harvesting 2D copper-cluster-based MOFs as efficient ROS generators for selective oxidation of amines","authors":"Huilin Huang, Qiong Yang, Kun Yao, Wen-Chao Geng, Xu Jing","doi":"10.1039/d5dt00120j","DOIUrl":"https://doi.org/10.1039/d5dt00120j","url":null,"abstract":"We have designed and synthesized an aesthetically appealing two-dimensional copper-cluster-based organic framework material named Cu-BPYC. This material exhibits superior charge separation and transfer efficiency, as well as reactive oxygen species (ROS) generation capability under visible-light irradiation. Through the synergistic mechanisms of photo-induced energy and charge transfer, it effectively promotes the oxidation of amines to imines. Additionally, Cu-BPYC demonstrates excellent structural stability and reusability in heterogeneous catalytic systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654235","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":"Metal complexes featuring organotellurium ligands: synthesis, coordination behavior, and applications","authors":"Sohan Singh, Nisha Yadav, Suman Mahala, Jatin Yadav, Kamalakanta Behera, Gyaneshwar Kumar Rao, Hemant Joshi, Kamal Nayan Sharma","doi":"10.1039/d4dt03502j","DOIUrl":"https://doi.org/10.1039/d4dt03502j","url":null,"abstract":"Organotellurium ligand-facilitated metal buildings were seen as profitable for catalytic activity, anti-cancer activities, and nanomaterial applications. A wide range of organotellurium ligands, including telluroethers, pincer-based frameworks, and tellurolates, have been extensively explored for their coordination with diverse metal centers. These ligands have been successfully complexed with base metals, platinum group metals, rare earth elements, and representative metals, providing a unified resource of literature on metal complexes of organotellurium ligands. The resulting metal-organotellurium complexes exhibit intriguing structural diversity and potential applications in catalysis, materials science, and coordination chemistry. Since 2005, a comprehensive review on the various applications of organotellurium ligands has yet to be available. Also, within the broader field of chalcogen chemistry, organotellurium ligands remain relatively less explored. This review focuses on the synthetic strategies and various applications of metal complexes containing organotellurium ligands, addressing a significant and critical gap existing in the literature. This review provides a comprehensive analysis of organotellurium ligands, focusing on their synthesis, structural diversity, and coordination chemistry. Beyond their fundamental significance, these ligands play a vital role in life sciences, nanochemistry, and materials science. Their catalytic proficiency is evident in essential organic reactions, including Suzuki-Miyaura and Mizoroki-Heck couplings, alcohol oxidation, C–N bond formation, aldehyde activation, and nitrophenol reduction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654239","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}
Olga Yu. Vassilyeva, Oksana V. Nesterova, Alina Bieńko, Urszula K. Komarnicka, Elena A. Buvaylo, Svitlana M. Vasylieva, Brian W. Skelton, Dmytro S. Nesterov
{"title":"Heterometallic CuCd and Cu2Zn complexes with o-vanillin and its Schiff-base derivative: slow magnetic relaxation and catalytic activity associated with Cu(II) centres","authors":"Olga Yu. Vassilyeva, Oksana V. Nesterova, Alina Bieńko, Urszula K. Komarnicka, Elena A. Buvaylo, Svitlana M. Vasylieva, Brian W. Skelton, Dmytro S. Nesterov","doi":"10.1039/d4dt03571b","DOIUrl":"https://doi.org/10.1039/d4dt03571b","url":null,"abstract":"In this work, two novel heterometallic mixed-ligand mixed-anion complexes [Cu<small><sup>II</sup></small>Cd<small><sup>II</sup></small>ClL(<em>o</em>-Van)(OAc)]·3H<small><sub>2</sub></small>O (<strong>1</strong>) and [Cu<small><sup>II</sup></small><small><sub>2</sub></small>Zn<small><sup>II</sup></small>Cl<small><sub>2</sub></small>L<small><sub>2</sub></small>(<em>o</em>-Van)(OAc)] (<strong>2</strong>) were prepared by reacting fine copper powder and Cd(<small>II</small>) or Zn(<small>II</small>) acetate with an ethanol solution of the Schiff-base ligand HL formed <em>in situ</em> in the condensation reaction of 2-hydroxy-3-methoxy-benzaldehyde (<em>o</em>-VanH) and CH<small><sub>3</sub></small>NH<small><sub>2</sub></small>·HCl. The compounds were thoroughly characterized by elemental analysis, FT-IR, UV/Vis and EPR spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction, revealing the neutral molecular nature of both the compounds. Catalytic properties of <strong>1</strong> and <strong>2</strong> were studied in the oxidation of hydrocarbons with H<small><sub>2</sub></small>O<small><sub>2</sub></small> under mild conditions, showing the maximum reaction rate of 4 × 10<small><sup>−5</sup></small> M s<small><sup>−1</sup></small> and TOF up to 640 h<small><sup>−1</sup></small>. Both compounds undergo complex transformations in solution as evidenced by kinetic analysis and time-dependent UV/Vis spectroscopy, indicating that the reduced Cu(<small>I</small>) form of <strong>1</strong> is unexpectedly unfavorable. Complex <strong>1</strong> demonstrates slow magnetic relaxation dominated by the direct relaxation process between <em>T</em> = 1.8 and 7 K under an external DC field of 0.2 and 0.4 T, a very rarely observable effect in the coordination compounds of Cu(<small>II</small>). Complex <strong>2</strong> possesses weak ferromagnetism (<em>J</em> = 4.50 cm<small><sup>−1</sup></small>, <em>zJ</em>′ = −0.201 cm<small><sup>−1</sup></small> for <em>H</em> = −<em>JS</em><small><sub>1</sub></small><em>S</em><small><sub>2</sub></small> formalism) occurring through the Cu–O–Cu pathways. Theoretical CASSCF, DFT and TDDFT calculations were applied to investigate the electronic structures of <strong>1</strong> and <strong>2</strong> and rationalize their behavior in solution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"56 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654238","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}
Sergey Volkov, Xia Yang, Vadim Kireev, Alexandru Banaru, Shujuan Han, Alevtina Gosteva, Maxim Arsentev, Dmitry Charkin, Alexey Povolotskiy, Yevgeny E. Savchenko, Maria Krzhizhanovskaya, Stepan Vorobiev, Yulia A. Vaitieva, Sergey Aksenov, Fangfang Zhang
{"title":"Expanding silver fluorooxoborate crystal chemistry: Ag2B5O8F with 3D double interpenetrating frameworks and Ag3B5O8F2 with 2D layers","authors":"Sergey Volkov, Xia Yang, Vadim Kireev, Alexandru Banaru, Shujuan Han, Alevtina Gosteva, Maxim Arsentev, Dmitry Charkin, Alexey Povolotskiy, Yevgeny E. Savchenko, Maria Krzhizhanovskaya, Stepan Vorobiev, Yulia A. Vaitieva, Sergey Aksenov, Fangfang Zhang","doi":"10.1039/d5dt00263j","DOIUrl":"https://doi.org/10.1039/d5dt00263j","url":null,"abstract":"The rapid development of the chemistry of fluorooxoborates is associated with their important role as valuable optical materials. In this work, we reported the first two silver representatives of the family, Ag2B5O8F (1) and Ag3B5O8F2 (2). Both structures are based on pentaborate groups with a different degree of “fluorination”: 1 contains interpenetrating frameworks composed of [B5O10F] fundamental building units, while 2 consists of layers of [B5O10F2]. The thermal expansion of 2 is strongly anisotropic, minimal in-plane (α11 = 13, α22 = –1 × 10−6 °C−1), and maximal in the normal direction (α33 = 42 × 10−6 °C−1). We also discussed the stereoisomerism of the [B5O10F2] pentaborate groups.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"69 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640144","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":"Correction: Dual role of arsenite in hydrolysis and post-hydrolysis fluorescence sensing of selective pH-dependent probes","authors":"Pushpendra Singh and Kalyan K. Sadhu","doi":"10.1039/D5DT90058A","DOIUrl":"10.1039/D5DT90058A","url":null,"abstract":"<p >Correction for ‘Dual role of arsenite in hydrolysis and post-hydrolysis fluorescence sensing of selective pH-dependent probes’ by Pushpendra Singh and Kalyan K. Sadhu, <em>Dalton Trans.</em>, 2024, <strong>53</strong>, 13950–13959, https://doi.org/10.1039/D4DT01728E.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 14","pages":" 5953-5953"},"PeriodicalIF":3.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt90058a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640369","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}
Ahmed Hassoon Mageed, Mohammed Tahir, Karrar Al-Ameed, Brian W. Skelton, Alexandre N. Sobolev, Murray V. Baker
{"title":"Synthetic and Structural Investigation of New Au(I) Complexes Featuring Bidentate Imidazole-2-thione Ligands","authors":"Ahmed Hassoon Mageed, Mohammed Tahir, Karrar Al-Ameed, Brian W. Skelton, Alexandre N. Sobolev, Murray V. Baker","doi":"10.1039/d5dt00483g","DOIUrl":"https://doi.org/10.1039/d5dt00483g","url":null,"abstract":"Gold(I) imidazole-2-thione (IMT) complexes [Au(IMT)2]+, [Au(diIMT)]+ or [Au2(diIMT)2]2+ were synthesized by reacting Au(SMe2)Cl with ligands containing one or two IMT groups. These AuI-IMT complexes were characterized by X-ray diffraction, NMR spectroscopy, and mass spectrometry. The IMT ligands provided a linear coordination array around the AuI center, with IMT C=S bonds orthogonal to the S-Au-S axis. In some cases for complexes of form [Au(IMT)2]+ and [Au(diIMT)]+, the cations aggregate to form dimeric or trimeric units in the solid state, and exhibit inter-cation Au...Au distances in the range ~3.03 - 3.07 Å, indicative of aurophilic interactions. The new AuI-IMT complexes exhibit NMR and mass spectra and that are generally consistent with the structures of cations of form [Au(IMT)2]+, [Au(diIMT)]+ or [Au2(diIMT)2]2+ as seen in the solid state. In two cases, however, 1H NMR spectra suggested mononuclear and dinuclear complexes [Au(diIMT)]+ and [Au2(diIMT)2]2+ existed in equilibrium, undergoing exchange reactions rapidly on the NMR timescale. Density functional theory (DFT) analysis supported the experimental conformations, showing agreement between the energetically favorable conformers and experimental structures. Photochemical and electrochemical properties were reported, with only one complex being strongly luminescent. The luminescence, at least in solution, did not appear to result from aurophilic interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"24 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640086","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}
Tiankun Zhao, Qi Zhang, Jialiu Zhao, Dongyu Mei, Jing Ma, Zhongduo Yang, Isabel Correia, Thomas Huhn, Sa-Hyun Kim
{"title":"Synthesis and X-ray Structure Analysis of Cytotoxic 2-Picolylamino type Hf IV-bis-Chelated Complexes","authors":"Tiankun Zhao, Qi Zhang, Jialiu Zhao, Dongyu Mei, Jing Ma, Zhongduo Yang, Isabel Correia, Thomas Huhn, Sa-Hyun Kim","doi":"10.1039/d4dt02859g","DOIUrl":"https://doi.org/10.1039/d4dt02859g","url":null,"abstract":"Eight novel heteroleptic Hf<small><sup>IV</sup></small> complexes containing differently substituted 2-picolylamino-<em>bis</em>-phenolate and 2,6-dipicolinic acid (Dipic) as chelating ligands were synthesized and characterized with yields higher than 80%. These [ONON] type Hf<small><sup>IV</sup></small> complexes have good aqueous stability and potent anti-tumor activity against Hela S3 (human cervical adenocarcinoma) and Hep G2 (human derived hepatoma) cells. In particular, the complexes demonstrated selective inhibitory activity against Hep G2 cells. The IC<small><sub>50</sub></small> of the most cytotoxic complex [L<small><sub>1</sub></small>Hf<small><sup>IV</sup></small>Dipic<small><sup>4-Cl</sup></small>] (0.9 ± 0.4 μM) was ten fold higher than that of cisplatin (11.2 ± 2.1 μM) on Hep G2 cells, being the most cytotoxic anti-tumor Hf<small><sup>IV </sup></small>complex to date. Furthermore, [L<small><sub>1</sub></small>Hf<small><sup>IV</sup></small>Dipic<small><sup>4-Cl</sup></small>] could inhibit tumor cell migration, induce reactive oxygen species generation (particullarly HO•), loss of mitochondrial membrane potential and almost exclusive early apoptosis in Hela S3 cells. [L<small><sub>1</sub></small>Hf<small><sup>IV</sup></small>Dipic<small><sup>4-Cl</sup></small>] exhibited rapid cellular uptake by Hela S3 cells, and when in aqueous media, these Hf<small><sup>IV</sup></small> complexes slowly hydrolyzed, releasing non-toxic phenolato ligands as the product of hydrolysis. Overall, these rare earth complexes, particularly [L<small><sub>1</sub></small>Hf<small><sup>IV</sup></small>Dipic<small><sup>4-Cl</sup></small>], show promising potential as novel anticancer agents with significant efficacy against human liver cancer cells and favorable selectivity profiles for further therapeutic development.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"55 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640192","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}
Jingqiu Li, Caiping Sheng, Ye Ma, Liangni Ban, Jie Zhu, Zhongping Huang, Hongxia Shen, Xuebo Cao, Longfeng Zhu
{"title":"Rapid synthesis of fault-free GME zeolite","authors":"Jingqiu Li, Caiping Sheng, Ye Ma, Liangni Ban, Jie Zhu, Zhongping Huang, Hongxia Shen, Xuebo Cao, Longfeng Zhu","doi":"10.1039/d5dt00508f","DOIUrl":"https://doi.org/10.1039/d5dt00508f","url":null,"abstract":"Optimization of the synthesis of known zeolite structures and discovery of their new applications are continuously the hot topics in the field of zeolite chemistry. One of the typical examples is GME zeolite structure. Herein, we for the first time report a rapid synthesis of fault-free GME zeolite by the combined strategy of seeding and aging. The fault-free GME zeolite could be obtained at 160 °C for only 2.5 h. Various characterization techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM) and nuclear magnetic resonance (NMR) have been used, which shows that the obtained product has good crystallinity, perfect hexagonal morphology, fully 4-coordinated Al species plus its fault-free feature. In addition, after the post-treatment of as-made GME zeolite, Na-GME zeolite with large BET surface area and high porosity could be obtained successfully. More importantly, the obtained Na-GME zeolite is firstly used for CO2 capture, giving the high CO2 adsorption of 5.37 mmol/g and excellently selective CO2 adsorption from CO2/N2 (15/85, v/v) with separation coefficient of 58.8. The fault-free GME zeolite used for CO2 capture might be potentially of significance for its industrial application.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640191","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":"In-situ Formed Ag Nanoparticle Decorated LiMn2O4 Cathodes with Outstanding Electrochemical Performance","authors":"Wangqiong Xu, Qiling Li, Shubiao Xia, Zhe Li, Feixiang Cheng, Shimei Guo","doi":"10.1039/d5dt00511f","DOIUrl":"https://doi.org/10.1039/d5dt00511f","url":null,"abstract":"Surface coating is an effective approach to realize the commercialization of cathode materials. By now, ionically conducting surface coatings are commonly used to improve the electrochemical stability of LiMn2O4. In this work, in-situ formed Ag nanoparticles with high electronic and ionic conductivity decorated LiMn2O4 cathodes are prepared via a simple calcination process. The detailed microstructural mechanism of the influence of Ag decorated on the electrochemical performance enhancement of spinel LiMn2O4 is uncovered by spherical-aberration-corrected (Cs-corrected) scanning transmission electron microscopy (STEM). The results demonstrate that Ag coating helps to promote the transport of Li+ and strengthen cycle stability by alleviating the decomposition of electrolyte and manganese dissolution. Accordingly, the capacity retention rate of the optimized 5wt% Ag/LiMn2O4 sample reached 80% after 900 cycles with an initial discharge-specific capacity of 100 mAh g-1 at 5 C (1 C = 148 mAh g-1). This work indicates that Ag coating is a promising technology for producing high-energy density lithium-ion batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"55 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640085","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":"Chromium Catalyzed Acceptorless Dehydrogenative (Cross)Coupling of Primary Amines to Secondary Imines","authors":"Aman Anand, Anitta Regina, Sachin Jalwal, Soumojyati Prodhan, Debangsu Sil, Manikandan Paranjothy, Subrata Chakraborty","doi":"10.1039/d4dt03460k","DOIUrl":"https://doi.org/10.1039/d4dt03460k","url":null,"abstract":"We present here acceptorless dehydrogenative coupling of primary amines to form secondary aldimines catalyzed by a complex of earth-abundant chromium. The reaction is promoted by Cr(DAFO)(CO)4 (DAFO = 4,5-diazafluorene-9-one) without using any additives, base or oxidant generating NH3 and H2 as sole by-products. Dehydrogenative cross-coupling of primary amines with aniline derivatives to unsymmetrical secondary imines was also achieved with good to excellent yields. A probable mechanism is proposed based on the stoichiometric investigation and computational studies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"39 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640087","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}