Dalton Transactions最新文献

{"title":"Precipitation of morphology-controlled uranium(VI) peroxide in nitric acid media","authors":"Lucas Muller, Paul Estevenon, Christelle Tamain, Nicolas Dacheux, Nicolas Clavier","doi":"10.1039/d4dt03467h","DOIUrl":"https://doi.org/10.1039/d4dt03467h","url":null,"abstract":"The precipitation of U(VI) peroxide (UO2(O2).4H2O, known as studtite) has been extensively studied in mildly acidic media (i.e. pH > 1). However, few studies have investigated the influence of highly acidic conditions (i.e. pH < 1) on the precipitation of studtite, particularly regarding the morphology of the final powder. The influence of high acidity (0.1 M < C(HNO3)ini < 2.0 M) and C(H2O2)ini/C(U)ini molar ratio (ranging from 10 to 70) on the precipitation kinetics, as well as the morphological and crystallographic properties of U(VI) peroxide was thus investigated in this study. Decreasing the acidity and increasing C(H2O2)ini/C(U)ini molar ratio significantly enhance both the final precipitation yield and the reaction kinetics. Furthermore, a correlation was established between the initial saturation index of the reaction mixture and the final morphology and crystallite size of the precipitated U(VI) peroxide, regardless of the initial precipitation conditions. These results demonstrate that in highly acidic nitric media, it is possible to control the morphology of the precipitated U(VI) peroxide by simply adjusting the initial saturation index. This correlation opens up interesting perspectives for the synthesis of powders with specific morphologies, particularly uranium peroxide or corresponding oxide powders obtained after thermal treatment. This morphology control is of great interest in the nuclear fuel fabrication field, as it allows obtaining oxide powders with optimized properties for sintering.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"40 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660773","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":"K2SO4(NH3SO3)2 and Cs2SO4(NH3SO3)3: Two Deep-UV Transparent Sulfamate-Sulfates with Moderate Birefringence","authors":"Yun Ji, Huili Zhang, Xin Wen, Jindong Chen, Guangsai Yang, Yuchen Yan, Guang Peng, Ning Ye","doi":"10.1039/d5dt00401b","DOIUrl":"https://doi.org/10.1039/d5dt00401b","url":null,"abstract":"In this work, polar tetrahedron [NH3SO3] and non-polar tetrahedron [SO4]2- were combined to synthesize two deep-UV transparent crystals K2SO4(NH3SO3)2 and Cs2SO4(NH3SO3)3 based on solution evaporation method. Due to the presence of two types of tetrahedral groups with wide bandgap and alkali metal cations without d-d or f-f transitions, both crystals exhibit a deep-UV cutoff edge, approximately 190 nm. Significantly, the birefringence of K2SO4(NH3SO3)2 and Cs2SO4(NH3SO3)3 are 0.0123 and 0.0153 @546 nm, respectively, which are remarkably improved compared to many conventional sulfate crystals. In addition, theoretical calculations were performed to analyze the relationships between the structures and optical properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"91 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654237","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":"Ca7Mg1.8Zn0.2Ga6O18:Bi3+/Mn4+ phosphor: energy transfer enables tunable colour emission and high sensitivity in optical thermometry","authors":"Gonggui Yan, Yuxuan Qi, Rihong Cong, Pengfei Jiang, Tao Yang","doi":"10.1039/d5dt00530b","DOIUrl":"https://doi.org/10.1039/d5dt00530b","url":null,"abstract":"Recent advancements in optical thermometry utilizing the fluorescence intensity ratio (FIR) technology have attracted tremendous attention in real-time temperature measurements due to its numerous advantages, such as high sensitivity. In this work, we rationally designed an FIR-type thermometer by utilizing the distinctive thermal responses of the blue and far-red emissions from Bi3+ and Mn4+ activators, respectively. To achieve a broad range of FIR values, we first optimized the blue emission of Ca7Mg2-xZnxGa6O18:0.05Bi3+ (CMZxGO:0.05Bi3+) through Zn2+-to-Mg2+ substitution and then utilized Bi3+/Mn4+ codoping into the optimal composition to realize dual emission. The blue emission of CMZxGO:0.05Bi3+ was improved significantly, which is associated with complex spectroscopic red and blue shifts due to the competitive effect of crystal field splitting and centroid shift for Bi3+-emitters. Additionally, Bi3+/Mn4+-codoped CMZ0.2GO:0.05Bi3+/yMn4+ phosphors exhibit tunable colour emission from blue to deep-red, arising from an increased energy transfer efficiency from Bi3+ to Mn4+ upon increasing the Mn4+-content. Benefitting from this energy transfer, Bi3+ and Mn4+ activators display severe thermal quenching and high thermal stability, respectively, thereby resulting in a high relative sensitivity (Sr) of 1.64% K-1 to temperature measurement. This Sr value surpasses that of most Bi3+/Mn4+- and Bi3+/Eu3+-codoped optical thermometers, implying the promising application potential of CMZ0.2GO:0.05Bi3+/0.001Mn4+ as an optical thermometer.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654203","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":"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}

{"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>^II</small>Cd<small>^II</small>ClL(<em>o</em>-Van)(OAc)]·3H<small>₂</small>O (<strong>1</strong>) and [Cu<small>^II</small><small>₂</small>Zn<small>^II</small>Cl<small>₂</small>L<small>₂</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>₃</small>NH<small>₂</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>₂</small>O<small>₂</small> under mild conditions, showing the maximum reaction rate of 4 × 10<small>⁻⁵</small> M s<small>⁻¹</small> and TOF up to 640 h<small>⁻¹</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>⁻¹</small>, <em>zJ</em>′ = −0.201 cm<small>⁻¹</small> for <em>H</em> = −<em>JS</em><small>₁</small><em>S</em><small>₂</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}

{"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}

{"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}

{"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>^IV</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>^IV</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>₅₀</small> of the most cytotoxic complex [L<small>₁</small>Hf<small>^IV</small>Dipic<small>^4-Cl</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>^IV</small>complex to date. Furthermore, [L<small>₁</small>Hf<small>^IV</small>Dipic<small>^4-Cl</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>₁</small>Hf<small>^IV</small>Dipic<small>^4-Cl</small>] exhibited rapid cellular uptake by Hela S3 cells, and when in aqueous media, these Hf<small>^IV</small> complexes slowly hydrolyzed, releasing non-toxic phenolato ligands as the product of hydrolysis. Overall, these rare earth complexes, particularly [L<small>₁</small>Hf<small>^IV</small>Dipic<small>^4-Cl</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}