Dalton Transactions最新文献

{"title":"Toward cationic gallium formazanate Lewis superacids.","authors":"Suhjung Chun, Erika L Fuller, Paul D Boyle, Joe B Gilroy","doi":"10.1039/d6dt02197b","DOIUrl":"10.1039/d6dt02197b","url":null,"abstract":"<p><p>Lewis superacids are a subclass of Lewis acids that garner attention for their high reactivity. We report gallium complexes supported by tetradentate formazanate ligands. Fluoride ion affinity calculations of the implicated four-coordinate cationic gallium formazanate cores revealed strong Lewis acidity, establishing a foundation for the development of gallium-based Lewis superacids.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13697-13701"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149029255","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":"Anomalous lattice contraction and optical properties in GaN:Nd³⁺ nanocrystals.","authors":"Agata Musialek, Robert Tomala, Wieslaw Strek","doi":"10.1039/d6dt01571a","DOIUrl":"10.1039/d6dt01571a","url":null,"abstract":"<p><p>This study reports on the anomalous lattice contraction and strain-engineered optical properties of GaN:Nd³⁺ nanocrystals (0.5-3%). The materials were synthesized using the sol-gel method and annealed in an ammonothermal process, demonstrating good crystalline quality with a pure hexagonal wurtzite structure. Despite the mismatch between the ionic radii of Ga³⁺ (0.62 Å) and Nd³⁺ (0.98 Å), X-ray diffraction analysis revealed an anomalous lattice contraction. This unique feature, attributed to the Gibbs-Thomson effect in nanocrystallites, induces compressive strain that overrides steric hindrance. The structural strain was found to directly modulate the optoelectronic properties, resulting in a linear blueshift of the optical energy gap (E_g) from 3.187 eV to 3.213 eV. Furthermore, optical analysis showed that UV excitation leads to energy transfer, resulting in bands arising from the f-f transitions of Nd³⁺ ions in the near-infrared range. The optimal concentration was determined to be 2% for Nd³⁺. These findings highlight the potential of Nd-doped GaN nanostructures for the development of advanced, strain-engineered optoelectronic devices.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13769-13777"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148965744","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":"Spontaneous formation of amorphous precursors and their vapour-induced crystallisation into zeolitic imidazolate frameworks.","authors":"Zilun Guo, Yuto Higuchi, Shunsuke Tanaka","doi":"10.1039/d6dt01866a","DOIUrl":"https://doi.org/10.1039/d6dt01866a","url":null,"abstract":"<p><p>In this study, a solvent-minimised synthesis method for ZIF-8 was developed based on vapour-induced crystallisation from a metal-organic ligand amorphous precursor that spontaneously forms under ambient conditions. An amorphous network was first formed by simply mixing a metal salt and an organic ligand without the use of a solvent. Subsequent exposure of the amorphous precursor to 1-butanol vapour induced its crystallisation into ZIF-8. Because the precursor is fluid and mouldable prior to crystallisation, it can be deposited and shaped into different morphologies, including particulate and continuous coatings. Variation of the metal source, imidazolate ligand, and amount of added 1-butanol revealed their respective roles in amorphous precursor formation and morphology control. As the crystallisation step requires only a limited amount of organic solvent supplied in vapour form, this approach may reduce liquid-solvent consumption compared with conventional solution-based MOF synthesis. This work provides a versatile route for the morphology-controlled synthesis of ZIF-based materials through spontaneously formed amorphous precursors.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149126108","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":"Stability of graphene-based single-atom catalysts across the first-row transition series: the interplay of coordination, composition, and metal identity.","authors":"Nathaniel A Balderramas Morgan, Alfonsina Cipollone, Alberto Sánchez López, Marcelo M Mariscal, Germán J Soldano","doi":"10.1039/d6dt01022a","DOIUrl":"10.1039/d6dt01022a","url":null,"abstract":"<p><p>The rational design of graphene-supported single-atom catalysts (SACs) requires maximizing metal utilization while ensuring structural stability, yet the underlying principles remain fragmented across the literature. Here we present a systematic DFT study of 60 SACs comprising first-row transition metals anchored to mono- and divacancy graphene supports, with and without nitrogen doping, and complemented by Ni(111)-supported metallic systems. By decomposing metal adsorption into deformation and intrinsic binding contributions, we distinguish structural from electronic metrics that contribute to the stability of these systems. Divacancies provide significantly stronger and more flexible coordination environments than monovacancies, and carbon coordination consistently outperforms nitrogen coordination regarding the metal-graphene bond. Across the transition-metal series, stability is primarily governed by the alignment between metal d states and the graphene Fermi level, further modulated by radius-dependent geometric accommodation. For the later transition metals, nitrogen doping weakens binding by partially filling antibonding states. Meanwhile, incorporation on a Ni(111) support enhances metal anchoring in divacancies but weakens it in monovacancies, while preserving the overall trends observed for unsupported systems. Magnetization and charge transfer are strongly correlated with the metal-graphene binding energies. Together, these trends define a categorical framework that intertwines the tendencies of vacancy topology, coordination chemistry, and electronic alignment. This understanding provides crucial insights for engineering robust graphene-based SACs and offers a basis for pre-selecting experimentally viable candidates.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13707-13719"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148890352","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":"Hydrogen-mediated structural and electronic stabilization of cubic perovskite SrLiH₃ under extreme compression.","authors":"Ertuğrul Karaca, Tarik Ouahrani, Daniel Errandonea","doi":"10.1039/d6dt01801g","DOIUrl":"10.1039/d6dt01801g","url":null,"abstract":"<p><p>This work presents a comprehensive first-principles investigation of the structural, mechanical, dynamical, vibrational, electronic, and bonding properties of SrLiH₃ under hydrostatic pressures up to 100 GPa. The relative stability of the cubic perovskite phase was evaluated against eight competing high-pressure candidate structures through enthalpy calculations. The results demonstrate that the cubic perovskite remains the thermodynamically favored phase throughout the investigated pressure range, with no pressure-induced structural transition. Mechanical stability is confirmed by the fulfillment of the generalized Born stability criteria, while phonon calculations reveal the absence of imaginary frequencies up to 100 GPa, establishing the dynamical stability of the structure. The pressure dependence of the infrared-active and silent phonon modes shows a systematic hardening of the high-frequency vibrations associated with the LiH₆ octahedra, indicating strengthened Li-H interactions under compression. Electronic structure calculations using the Heyd-Scuseria-Ernzerhof hybrid functional predict that SrLiH₃ remains an insulator, with the band gap increasing from 2.7 eV at ambient pressure to 3.3 eV at 100 GPa. Quantum theory-based analysis of the atomic basins reveals a pronounced contraction with increasing pressure, while the calculated atomic charges show only moderate changes and retain the clear charge separation between the cationic Sr and Li atoms and the anionic H atoms. Because the hydrogen sublattice occupies the largest fraction of the atomic volume, it makes the dominant contribution to the overall compressibility. These findings indicate that the predominantly ionic nature of cubic SrLiH₃ is preserved under compression, with the pressure response governed mainly by the collective contraction of the atomic basins rather than by significant pressure-induced charge redistribution. The combined thermodynamic, mechanical, vibrational, electronic, and topological analyses consistently indicate that cubic perovskite SrLiH₃ exhibits remarkable structural robustness and enhanced electronic stability under extreme compression, making it a promising model system for understanding the behavior of ionic complex hydrides at high pressure.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13888-13901"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149011692","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":"Pressure-induced structural evolutions and electronic properties of Eu³⁺ and Pr³⁺ doped yttrium oxide crystals: a comparative study.","authors":"Xinyu Lv, Ruiqi Xiong, Meng Ju, Mingmin Zhong, Peng Wang, Yang Xiao, Weiguo Sun, Yuanyuan Jin, Chuanzhao Zhang","doi":"10.1039/d6dt02053d","DOIUrl":"10.1039/d6dt02053d","url":null,"abstract":"<p><p>Rare-earth-doped yttrium oxide (Y₂O₃) is a promising optoelectronic material due to its outstanding optical characteristics, including the efficient red emission of Eu³⁺ and the lattice-sensitive luminescence of Pr³⁺. The crystal lattice and structural information have aroused widespread interest. However, clarifying the structural evolution and local structures in doped systems under high pressure remains challenging. In this work, we systematically investigate the structural evolution and electronic properties of Y₂O₃:Eu³⁺ and Y₂O₃:Pr³⁺ under the pressure range of 0-40 GPa. The ground-state structures are identified for the first time. Eu³⁺ and Pr³⁺ substitute Y³⁺ sites with a doping concentration of 3.125%. At ambient pressure, the structure of Y₂O₃:Eu³⁺ exhibits a trigonal structure with the <i>R</i>3̄ space group while Y₂O₃:Pr³⁺ exhibits a monoclinic configuration with the <i>P</i>2 space group. LDA + U + SOC calculations reveal narrowed band gaps of 1.884 and 3.326 eV for Y₂O₃:Eu³⁺ and Y₂O₃:Pr³⁺, respectively, indicating an insulator-to-semiconductor transition. Under pressure, Y₂O₃:Eu³⁺ shows higher sensitivity in lattice and electronic properties than Y₂O₃:Pr³⁺. Pressure enhances intrinsic 4f-electron differences, leading to divergent evolution trends. The 4f configuration serves as a key controller of high-pressure behavior. These findings could not only provide important information for further investigations of rare-earth-doped systems, but also help to gain more insights into designing a new generation of laser materials under extreme conditions.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13829-13838"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148987175","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":"Tuning photochromism in multivariate zinc dipyridyl-naphthalenediimide coordination polymers.","authors":"Adnan Ishaq, Louise Male, Neil R Champness","doi":"10.1039/d6dt02007k","DOIUrl":"10.1039/d6dt02007k","url":null,"abstract":"<p><p>Multivariate compositions of zinc halide dipyridyl-naphthalenediimide coordination polymers are shown to directly tune photochromic response through modification of halide lone pair-NDI LUMO overlap.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"13931-13935"},"PeriodicalIF":3.3,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13592237/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149011707","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":"Homoleptic oligothienyl-substituted bis(terpyridine) Ir(III) and Ru(II) complexes: synthesis, photophysics, and anticancer and antimicrobial photodynamic therapeutic effects","authors":"Kalara D Gamage,Zilun Lian,Giulia Kassab,Ge Shi,Md Razzak,Abbas Vali,Kuo-Hao Chen,Alisher Talgatov,Juan Chen,Svetlana Kilina,Gang Zheng,Sherri Ann McFarland,Wenfang Sun","doi":"10.1039/d6dt01203e","DOIUrl":"https://doi.org/10.1039/d6dt01203e","url":null,"abstract":"Four homoleptic bis(terpyridine) Ir(III) and Ru(II) complexes bearing oligothienyl substituents on both tpy ligands (M(nT-tpy)2, M = Ir, Ru; n = 3, 4) were synthesized and characterized to evaluate their photophysical properties, including UV–Vis absorption, emission, and transient absorption, and photodynamic therapeutic (PDT) effects toward melanoma cells and Gram-positive Staphylococcus aureus and Gram-negative P. aeruginosa bacteria. The UV-Vis absorption studies revealed that the low-energy absorption bands at >350 nm red-shifted as the number of thienyl rings increased. Additionally, the Ru(II) complexes displayed further red-shifts alongside increased molar extinction coefficients. All complexes exhibited phosphorescence in the NIR region with lifetimes spanning from 1.4 μs to 7.4 μs in DMSO. These long-lived triplet excited states resulted in efficient singlet oxygen generation (ΦΔ = 0.30–0.69), with Ru complexes being more effective singlet oxygen generators than their Ir analogues. Oligothienyl chain extension primarily tuned the ligand-centered redox behavior of both the Ir(III) and Ru(II) complexes, shifting oligothienyl oxidation cathodically and oligothienyl reduction anodically. It had little effect on the Ru2+/Ru3+ oxidation or the terpyridine-centered reduction potentials, while no Ir3+/Ir4+ oxidation was observed within the potential window examined. In vitro PDT studies demonstrated strong photocytotoxicity under normoxia and hypoxia towards SKMEL28 melanoma cells, with Ir(4T-tpy)₂ emerging as the most promising PDT agent among these four complexes. These complexes also exhibited potent light-activated antibacterial activity against Staphylococcus aureus at nanomolar concentrations, with Ru(3T-tpy)2 showing the strongest aPDT effect, surpassing that of the most commonly used antimicrobial photosensitizers. Ir(3T-tpy)2 also induced complete inactivation of Gram-negative Pseudomonas aeruginosa bacteria at 10 μM with 5 J/cm2 light dosage. These results highlight the potential of M(nT-tpy)2 as photosensitizers for both cancer and antimicrobial photodynamic therapy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067378","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":"Broadband red-emitting one-dimensional halide (C3H8N6)2MnCl6 with a high photoluminescence quantum yield","authors":"Yingxing Luo,Yan Song,Mingxing Chen,Xinfang Wang,Zhigang Wang,Yanxia Wang,Danyang Li,Zhen Jia,Mingjun Xia","doi":"10.1039/d6dt02135b","DOIUrl":"https://doi.org/10.1039/d6dt02135b","url":null,"abstract":"Organic-inorganic hybrid metal halides (OIHMs) have emerged as highly promising optoelectronic materials for light-emitting diodes, fluorescence sensing, and radiation detection due to their structurally tunable crystal structures and excellent photophysical properties. In particular, manganese-based OIHMs have attracted extensive attention because of their characteristic broadband d - d emission, environmental benignity, and low fabrication cost. Herein, a novel one-dimensional (1D) Mn-based OIHM (C3H8N6)2MnCl6 was successfully synthesized via a facile aqueous solution method. (C3H8N6)2MnCl6 crystallizes in the P21/m space group and features 1D [〖Mn〗_n 〖Cl〗_(5n+1) ]_∞^((3n+1)-) chains constructed of vertex-sharing [MnCl6]4- octahedra, which are further isolated by [C3H8N6]2+ cations. The (C3H8N6)2MnCl6 crystals display a broad excitation band spanning 240 - 600 nm with a maximum at 415 nm and emit broadband red emission covering 540 - 870 nm peaking at 665 nm. The photoluminescence quantum yield (PLQY) of (C3H8N6)2MnCl6 crystals is up to 78.82%, which is significantly higher than that of the constituted organic component melamine (5.38%). Mechanistic studies demonstrate that the red luminescence originates from the spin-forbidden d-d electron transitions of the [MnCl6]4- octahedra, and the 1D chain structure facilitates exciton localization, benefiting broadband emission and high PLQY. Meanwhile, the high thermal activation energy of 141.8 meV suppresses thermally activated exciton dissociation at room temperature, thereby favouring efficient radiative recombination. This work not only enriches the structural family of Mn-based OIHMs but also provides a feasible strategy for the design of high-efficiency red-emitting luminescent materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067377","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 Pentacoordinated Arsenic(V) Dication Stabilized by Intramolecular Donor Coordination","authors":"Taiki Adachi,Tomoki Yasui,Showa Kitajima,Chihiro Okochi,Kenji Kanaori,Hitoshi Kasai,Kouki Oka,Takahiro Iwamoto,Kensuke Naka,Hiroaki Imoto","doi":"10.1039/d6dt01928e","DOIUrl":"https://doi.org/10.1039/d6dt01928e","url":null,"abstract":"We report the design, synthesis, and comprehensive characterization of a novel intramolecularly pentacoordinated arsenic(V)-centered dication, [Ph(ppy)2As]2+ ([2]2+; ppy = 2-(2-pyridyl)phenyl). The neutral precursor Ph(ppy)2As (2) was prepared from nonvolatile arsenic sources, and subsequent oxidation afforded the dicationic species [2][PF6]2. Single-crystal X-ray diffraction analysis revealed that oxidation strengthens intramolecular As–N coordination, leading to a slightly distorted trigonal–bipyramidal geometry. Despite its dicationic and electrophilic character, [2]2+ exhibits remarkable thermal and hydrolytic stability, attributable to its robust intramolecular chelation. Treatment with NaOH and NaOMe affords hexacoordinated hydroxide and methoxide adducts, respectively, whereas reactions with external neutral Lewis bases are inhibited by steric shielding. Fluoride-ion affinity calculations revealed that the pentacoordinated [2]2+ exhibits consistently higher fluoride affinity than the hexacoordinated analogue [1]2+ in both the gas phase and solvent-corrected calculations. This study demonstrates that intramolecular pentacoordination provides an effective structural platform for balancing the stability and accessible reactivity of arsenic(V) dications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"35 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067379","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}