Dalton Transactions最新文献

{"title":"Comparative study of the direct and photocatalytic light activation of platinum(IV) prodrugs","authors":"Kinjal Mileche,Susana Huaman,Ke Wu,Jake Vickery,Hannah Coxhead,Alexander N. Smith-Wu,Patricia Juhl Allworthy,Jovana Katrinka Mavrak,Aminesena Baser,Safacan Kolemen,Manuel Muller,Mahvash Tavassoli,Ismael Perez,Eleanor Stride,John F Callan,Adam Charles Sedgwick","doi":"10.1039/d6dt01745b","DOIUrl":"https://doi.org/10.1039/d6dt01745b","url":null,"abstract":"Here, we present a comparative study of direct and photocatalyst-mediated photoactivation of reporter-functionalised Pt(IV) prodrugs, Carbo-4NP and CarboNap. Direct blue-light irradiation and green-light activation using the photocatalyst Rose Bengal both achieved rapid and complete Pt(IV) reduction in solution, monitored by UV-vis and fluorescence spectroscopy. Translation to live cells revealed a marked divergence between the two approaches. Direct blue light (415 nm) photoactivation produced >300-fold enhancement in fluorescence intensities upon probe activation and >10-fold in cytotoxicity. Photocatalytic activation was considerably less effective in cells despite its excellent solution-phase performance. These findings identify direct photoactivation as the superior strategy for intracellular activation of Pt(IV) prodrugs and support the further development of direct light-activated platinum therapeutics.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151905","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":"New hydrophilic triple-charged cationic receptors for binding pertechnetate and perrenate anions in acidic aqueous solutions","authors":"Yuri Ustynyuk,Igor P. Gloriozov,Zoia Sizova,Nelly Zhokhova,Alisultan R Alisultanov,Anna Fominykh,Uliana Leksina,Petr I. Matveev,Alexander Gopin,Vladimir G. Petrov,Viktor Tafeenko,Valentine Nenajdenko","doi":"10.1039/d6dt01851c","DOIUrl":"https://doi.org/10.1039/d6dt01851c","url":null,"abstract":"One of the most complex and still unresolved problems in spent nuclear fuel (SNF) reprocessing is the separation of 99Tc (a β-emitter, t½ = 2.13×10⁵ years). Technetium is one of the most environmentally hazardous radionuclides contained in SNF in the form of the pertechnetate anion TcO₄⁻. Many researchers around the world have been working for the past 30 years to create highly selective molecular receptors for its binding in aqueous solutions. In this study, we synthesized and thoroughly characterized a large series of new receptors containing three cationic pyridinium moieties. The structures of these compounds and their complexes with TcO₄⁻ and ReO₄⁻ anions were studied using a combination of physicochemical methods (X-ray diffraction, NMR, and mass spectrometry) coupled with quantum-chemical modeling based on density functional theory (DFT). Extraction tests of the new receptors showed that they effectively suppress TcO₄⁻ transfer into the organic phase during uranium and plutonium extraction using both the TODGA/F-3 and TBP/kerosene systems, opening up prospects for their use as hydrophobic masking agents for TcO₄⁻ binding in nitric acid during SNF reprocessing.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"158 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151907","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 Highly Luminescent Zero-Dimensional Hybrid Tin(II) Bromide for White-Light Emission","authors":"Jie Chen,Jiangchun Xing,Xiao-Fan Zhang,Yibo Xu,Guoming Lin,Zhuoyuan Li,Xin-Yi Zhang,Chunqing Ji,Yuyin Wang,De-Long Liu","doi":"10.1039/d6dt02278b","DOIUrl":"https://doi.org/10.1039/d6dt02278b","url":null,"abstract":"Lead-free zero-dimensional (0D) Sn(II) halides are promising broadband emitters, but achieving high efficiency while retaining practical device performance remains challenging. Here, we report [PPAA] 2 [SnBr 6 ]Br 2 , comprising triprotonated 3-(piperazin-1-yl)aniline ([PPAA] 3+ ) cations, discrete distorted Sn-Br coordination environments, and two noncoordinating charge-balancing bromide ions. Analysis of the six nearest Br neighbors gives a bond-length distortion index of 8.43 × 10 -4 and a nearest Sn•••Sn separation of 9.004 Å. N-H•••Br contacts connect the organic cations to both Sn-associated and noncoordinating bromides. The crystals emit at 554 nm with a full width at half-maximum of 106 nm and an absolute photoluminescence quantum yield of 80.9%. Combining this yield with the 1.48 μs lifetime gives effective radiative and nonradiative rates of 5.47 × 10 5 and 1.29 × 10 5 s -1 , respectively, under a single-population approximation. Temperature-dependent emission gives an apparent thermal-quenching activation energy of 178.8 meV. The spectroscopy is consistent with self-trapped-exciton-like emission, while ground-state calculations support a contribution from the inorganic units. A phosphor-converted white LED gives chromaticity coordinates of (0.33, 0.33) and a color rendering index of 95. These results connect local coordination, hydrogen-bond contacts, and radiative branching in an efficient lead-free yellow phosphor.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"157 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151902","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":"Low thermal quenching of a 3D Ag-MOF with 2D inorganic layers and π-conjugated skeletons for light-emitting diode","authors":"Honghong Lan,Jiange Wang,Weizhou Wang,Shao-Bin Miao,Xiao-Gang Yang","doi":"10.1039/d6dt01998f","DOIUrl":"https://doi.org/10.1039/d6dt01998f","url":null,"abstract":"Developing phosphor materials with desirable thermal quenching resistance for phosphor-converted light-emitting diodes (PC-LEDs) is still a formidable challenge. Herein, a Ag-based 3D metal-organic framework [AgNO3(BTD)0.5] (1) was facilely synthesized at room temperature with the presence of 2,1,3-benzothiadiazole (BTD) electron acceptor. This complex exhibits alternating arrangement of inorganic silver nitrate layers and organic BTD π-conjugated chains. Meanwhile, the BTD π-conjugated moieties are anchored via coordination bonds, π•••π stacking, hydrogen bonds, and chalcogen bonds, which collectively construct a compact network architecture. It shows intensive yellow-orange emission with a long lifetime of 81 μs. Thermal quenching measurements confirm that this complex only undergo luminescence losses of 5.91% relative to room temperature at 150 °C. The successful fabrication and operation of PC-LED device verify potential application of this complex in solid state lighting.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"471 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151910","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":"Recent advances in cobalt group metal complexes as anticancer agents: Influence of ligands on therapeutic efficacy","authors":"Nisha Yadav,Anjali Anjali,Sanjana Sanjana,Vaani Sharma,Kamal Nayan Sharma,Chandra Mohan Srivastava,Pooja Rawat,Indresh Kumar Pandey,Umesh Nath Tripathi,Gyandshwar Kumar Rao","doi":"10.1039/d6dt00899b","DOIUrl":"https://doi.org/10.1039/d6dt00899b","url":null,"abstract":"Following the groundbreaking discovery of cisplatin as a potent anticancer agent, transition metal complexes have garnered significant interest for their potential in therapeutic applications. Among these, cobalt group metals; cobalt (Co), rhodium (Rh), and iridium (Ir); have emerged as particularly promising candidates for the development of novel anticancer drugs. Their appeal lies in their ability to adopt multiple oxidation states, exhibit rich coordination chemistry, and undergo redox reactions, all while interacting favorably with biological targets. Notably, the nature of ligands coordinated to the metal center plays a crucial role in modulating the complex’s electronic structure and, consequently, its anticancer efficacy. This review presents a comprehensive overview of recent advancements over the past decade, with particular emphasis on the structural diversity of cobalt group complexes arising from varied ligand environments and their corresponding therapeutic potential against a range of cancer types.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151908","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":"Bismuth flavonol complexes: investigating membrane permeability and activity in human colorectal cancer cells","authors":"Serafina M. C. Crapis,Stephen A. Holt,Philip C. Andrews,Kirralee J. Burke,Ronald Sluyter,Carolyn T. Dillon","doi":"10.1039/d6dt00701e","DOIUrl":"https://doi.org/10.1039/d6dt00701e","url":null,"abstract":"In this study the biological activity of novel bismuth-flavonol (BiFlav) complexes has been explored in colorectal cancer cells to determine their potential as anti-cancer therapeutic agents. The work derives from the fact that dietary flavonols exhibit well established anti-oxidant and anti-cancer properties while bismuth compounds are marketed for gastrointestinal therapy. The membrane permeability properties and in vitro anti-cancer activities of heteroleptic and homoleptic BiFlav complexes (BiPh(Flav)2, BiPh(BrFlav)2 and Bi(BrFlav)3; Ph = phenyl, Flav = 3-hydroxyflavone, BrFlav = 4-bromo-3-hydroxyflavone), are presented. Electrochemical impedance spectroscopy and neutron reflectometry studies revealed significant alterations in membrane structure, especially by BiPh(Flav)2. Cellular uptake studies (performed by graphite furnace atomic absorption spectroscopy) across human colorectal cancer (CRC) cell lines (HCT-8, HCT-116, and HT-29) showed cell-specific differences in bismuth accumulation, with BiPh(Flav)2 exhibiting the highest cellular uptake and retention. MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide) assays showed significantly greater toxicity (lower IC50 values) of BiFlav complexes compared to the free flavonols. BiPh(Flav)2 demonstrated the highest cytotoxicity, particularly in HCT-116 cells (2.63 µM), followed by HT-29 (6.57 µM) and HCT-8 (8.92 µM). Brominated derivatives, such as BiPh(BrFlav)2 and Bi(BrFlav)3, which exhibited membrane retention, showed only moderate cytotoxicity (8.42 µM and 26.2 µM respectively, HCT-8 cells). MTT assays were also conducted with human peripheral blood mononuclear cells (PBMCs) where BiPh(BrFlav)2 demonstrated reduced cytotoxicity (23.3 µM) and favourable selectivity indices (>2) across CRC cell lines. These findings highlight the therapeutic potential of BiFlav complexes through multi-faceted mechanisms involving both membrane disruption and intracellular interactions, offering a foundation for their further investigation for targeted colorectal cancer therapy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151909","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 reactivity of boron-substituted silyllithium as a nucleophilic Si-B unit.","authors":"Sho Hirotani, Yuta Kowada, Ko Tanaka, Yuya Kadota, Souichiro Toyomori, Masaaki Nakamoto, Hiroto Yoshida, Shogo Morisako, Atsushi Kawachi","doi":"10.1039/d6dt02205g","DOIUrl":"https://doi.org/10.1039/d6dt02205g","url":null,"abstract":"<p><p>Boron-substituted silyllithium was synthesized <i>via</i> Sn-Li exchange between the corresponding (boryl)silylstannane and <i>n</i>-BuLi and reacted with chlorosilanes to afford a series of Si-B-containing di-, tri-, and tetrasilanes. The tri- and tetrasilane derivatives were examined by UV-vis spectroscopy and density functional theory calculations to assess the electronic consequences of boron incorporation into σ-conjugated silane frameworks. In addition, the diaminoboryl moiety bound to boron can be selectively transformed into a pinacolatoboryl group without Si-B bond cleavage. Overall, this work provides a chemically intuitive entry to Si-B-containing oligosilanes and enables systematic investigation of boron incorporation into σ-conjugated silane frameworks.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163594","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":"Intrinsic incomplete spin crossover in [Fe(L^R)₂(NCS)₂] complexes bearing 4-alkylated <i>N</i>-(2-pyridylmethylene)aniline ligands.","authors":"Shin-Ichiro Takeshi, Satomi Watanabe, Masataka Mitsui, Rina Takano, Takayuki Ishida","doi":"10.1039/d6dt01438k","DOIUrl":"https://doi.org/10.1039/d6dt01438k","url":null,"abstract":"<p><p>A series of iron(II) complexes, [Fe(L^R)₂(NCS)₂] (L^R = 4-alkyl-<i>N</i>-(pyridin-2-ylmethylidene)aniline; R = linear alkyl from methyl to <i>n</i>-hexyl), exhibit stepwise and/or incomplete spin-crossover (SCO) behavior. In most cases, the crystals contain two crystallographically independent molecules at 300 K, indicating site-selective SCO that accounts for two-step transitions. When the residual high-spin fraction falls below 50%, additional symmetry breaking is required, leading to an increased number of inequivalent Fe sites. The ethyl derivative undergoes a solid-state phase transition from <i>P</i>2₁/<i>n</i> (<i>Z</i>' = 2) at high temperature to <i>Pn</i> (<i>Z</i>' = 4) at low temperature, where three low-spin (LS) and one high-spin (HS) Fe sites coexist. In contrast, one crystallographically independent site in the methyl derivative becomes an approximately equally populated HS/LS disordered site, whereas the other adopts the LS state at low temperature while retaining the <i>Pbca</i> (<i>Z</i>' = 2) space group throughout the transition. Together with the intermediate Fe-N bond lengths observed for the <i>n</i>-hexyl derivative, these findings support the interpretation that the observed mixed-spin sites are most reasonably explained by local HS/LS coexistence rather than genuine intermediate-spin states. These findings point to a symmetry-lowering-driven mechanism for multistep and incomplete SCO, including cases in which the symmetry reduction remains crystallographically unresolved.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134317","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":"Decoration of N-heterocyclic cores with bisphosphonates: synthetic access to mono- and di-substituted s-triazine linkers, and their structurally diverse coordination networks.","authors":"Elpiniki Chachlaki, Duane Choquesillo-Lazarte, Konstantinos D Demadis","doi":"10.1039/d6dt00901h","DOIUrl":"https://doi.org/10.1039/d6dt00901h","url":null,"abstract":"<p><p>The synthesis and characterization of six new phosphonate linkers and their coordination networks are reported in this paper. All have the s-triazine heterocyclic core as a common structural feature and display mono- or di-substitution by aminoalkyl-phosphonate grafts. The phosphonate-bearing, amine-containing nucleophiles used for the substitution were amino-bis(methylenephosphonate) (ABMP), (3-amino-1-hydroxypropane-1,1-diyl)bis(phosphonic acid) (pamidronate, PAM), (4-amino-1-hydroxy-1-phosphonobutyl)phosphonic acid (alendronate, ALE), and (6-amino-1-hydroxyhexane-1,1-diyl)bis(phosphonic acid) (neridronate, NER). ABMP features a secondary amine, and PAM, ALE, and NER feature primary amines. The products isolated were Tr-1ABMP, Tr-1PAM, Tr-2PAM, Tr-1ALE, Tr-2ALE, and Tr-2NER (Tr = triazine; the numbers 1 and 2 indicate mono- and di-substitution). These ligands were used to synthesise coordination networks with alkaline earth metal ions. The crystal structures of three derivatives, namely Sr-Tr-1ABMP (2D), Ca-Tr-1PAM (1D), and Sr-Tr-2NER (1D), reveal the rich coordination chemistry and potential of these ligands. Tr-1PAM and Tr-2NER use only their phosphonate moieties for coordination, whereas Tr-1ABMP employs also the N and O atoms from the triazine ring. None of the structures display π-π stacking interactions. The structures of the metal derivatives are analysed and compared to several triazine-containing literature examples to determine the electronic and protonation state of the triazine ring. The triazine ring and external N atoms in the compounds Ca-Tr-1PAM, Sr-Tr-1ABMP, and Sr-Tr-2NER are planar, in agreement with the extended planarity concept. The protonation state of the triazine ring depends on the synthesis pH. The triazine ring is neutral (non-protonated) in Sr-Tr-1ABMP, but one of the N atoms is protonated in Ca-Tr-1PAM and Sr-Tr-2NER. This research establishes a promising entry to the coordination chemistry of phosphonate-substituted triazine rings. Such ligands can enrich the phosphorus synthetic chemist's \"toolbox\" for the creation of new coordination networks with diverse structure types.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134254","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":"Green and sustainable synthesis of nanostructured metal phosphates: structure-property relationships and catalytic applications.","authors":"Sreenivasulu Peta, Kiran Sagar Unikela","doi":"10.1039/d6dt01540a","DOIUrl":"https://doi.org/10.1039/d6dt01540a","url":null,"abstract":"<p><p>The sustainable design of effective catalysts necessitates synthetic methods that reduce resource usage while ensuring precise control over the composition, structure, and accessibility of active sites. Metal phosphates represent a versatile category of materials, as phosphate groups can directly engage in framework construction, influence the coordination and electronic environment of metal centers, and enhance acid-base, adsorption, and redox characteristics. This review thoroughly evaluates environmentally friendly and sustainable methods for synthesizing nanostructured metal phosphates, including hydrothermal, microwave-assisted, precipitation and co-precipitation, ultrasound-assisted, template-directed, mechanochemical, and solvent-free techniques. Instead of viewing individual studies as separate instances, the review analyzes how synthesis conditions affect nucleation, crystallization, morphology, porosity, defect formation, and multimetallic interactions, as well as how these structural attributes influence catalytic performance. Particular attention is devoted to the mechanistic role of phosphate species in material formation and catalysis, encompassing M-O-P bond formation, framework charge balance, template interactions, stabilization of metal centers, and modulation of Brønsted/Lewis acidity and redox behavior. The review critically assesses the advantages and limitations of nanoparticle, nanoporous, and hybrid architectures concerning active-site accessibility, mass transport, stability, leaching, and scalability. Finally, it highlights significant knowledge gaps, such as the identification of genuine active sites, <i>operando</i> structural evolution, quantitative structure-activity relationships, defect control, multimetallic synergy, and standardized sustainability evaluation. Thus, the review establishes a structure-mechanism-performance framework for the rational development of scalable and truly sustainable phosphate-based nanocatalysts.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134257","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}