Inorganic Chemistry Frontiers最新文献

{"title":"Highly active superoxide dismutase mimic: pyridine-carboxamide based copper(II) complexes","authors":"Róbert Diószegi, Andrea Guidetti, Norbert Ág, Ilenia Serra, Dóra Vargáné Szalóki, Dóra Bonczidai-Kelemen, Nóra May, Erzsébet Fekete, Levente Karaffa, István Fábián, Sabine Van Doorslaer, Norbert Lihi","doi":"10.1039/d5qi01687h","DOIUrl":"https://doi.org/10.1039/d5qi01687h","url":null,"abstract":"Pyridine-based ligands functionalized with one (PyHis) or two histidine (PydiHis) moieties have been synthesized, and their copper(II) complexes were studied as novel antioxidant systems. The complexes were characterized by pH-potentiometric, spectroscopic (UV-vis, circular dichroism, continuous-wave and pulsed electron paramagnetic spectroscopy (EPR)), computational (DFT) and X-ray diffraction methods. The complexes show high thermodynamic stability. The PyHis complex possesses a (COO <small>^-</small>,N <small>_py</small> ,N <small>^-</small>,N <small>_Im</small> ) donor set, while PydiHis binds copper(II) via the (N <small>_Im</small> ,N <small>_py</small> ,N <small>^-</small>,N <small>_Im</small> ) donor set at physiological pH. The PyHis and PydiHis complexes of copper(II) exhibit negligible (IC <small>₅₀</small> = 147 ± 15 µM) and outstanding (IC <small>₅₀</small> = 0.64 ± 0.07 µM) superoxide dismutase (SOD) activity, respectively. The noted difference is attributed to the structural flexibility of the latter complex as confirmed by pulsed EPR spectroscopy. The antioxidant activity of the copper(II) complexes was also tested in vivo by monitoring their effects on the mycelial growth of Aspergillus niger under oxidative stress. Both complexes were able to protect the cells under these conditions, however, the copper(II) complex of PydiHis was more effective in accordance with its excellent SOD activity. Consequently, the copper(II) complex of PydiHis stands out as efficient, low-molecular weight SOD mimic combining high catalytic activity with proven biological efficacy under oxidate stress conditions making it a promising candidate for medical applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermally Responsive Magnetic Bistability Through Solid-Liquid Phase Transitions in Alkylthio-Functionalized Dithiadiazolyl Radicals","authors":"Juho M Toivola, Ankita Naik, Manu Lahtinen, Oriol Gonzàlez-Prats, Andrea Perez Prieto, Itziar Oyarzabal, Aaron M. Mailman","doi":"10.1039/d5qi01391g","DOIUrl":"https://doi.org/10.1039/d5qi01391g","url":null,"abstract":"A series of p-alkylthio-substituted phenyl-1,2,3,5-dithiadiazolyl radicals, p-R-PhDTDA (R = SMe (2), SEt (3), S n Pr (4), S i Pr (5), S t Bu ( 6)), and the prototypical (R = H (1)) phenyl derivative exhibit a thermally driven solid-liquid transition accompanied by a spin-state change from diamagnetic (S = 0) π-dimers to paramagnetic (S =½) radicals. X-ray crystallography reveals that most derivatives form phase-pure cis-cofacial dimers, except 3 which crystallizes as three distinct polymorphs: 3α displays a sandwich-type herringbone structure stabilized by intermolecular S••••S chalcogen bonding (isostructural with 2) while 3β and 3γ feature slipped π-stacked herringbone arrangements (ABAB and AA'BB', respectively). In these latter forms, the alkyl groups act as steric buffers between adjacent stacks, a structural motif retained in derivatives 4 -6. Differential scanning calorimetry (DSC), hot-stage microscopy, and vibrating sample magnetometry (VSM) collectively demonstrate a hysteretic phase transition in 1 -6 with magnetic bistability arising from supercooling of the paramagnetic liquid phase. These results establish a new design paradigm for stimuli-responsive materials in which molecular packing, thermal behavior, and spin states are intrinsically linked through phase transitions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"104 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Realizing large birefringence via S-substitution and anisotropic arrangement optimization","authors":"Zhiwei Sun, Bingbing Wu, Zihao Yu, Qingran Ding, Yuling Wang, Ming Zhong, Sangen Zhao, Junhua Luo","doi":"10.1039/d5qi01600b","DOIUrl":"https://doi.org/10.1039/d5qi01600b","url":null,"abstract":"Despite the widespread use of birefringence crystals in optical instruments, the birefringence of commercially available crystals is generally limited (Δ<em>n</em> &lt; 0.3), making them less suitable for demanding optical requirements. In this work, three novel birefringent crystals, namely (C<small>₂</small>N<small>₅</small>H<small>₈</small>)(H<small>₂</small>C<small>₃</small>N<small>₃</small>O<small>₃</small>)·H<small>₂</small>O (<strong>1</strong>), (C<small>₂</small>N<small>₅</small>H<small>₈</small>)<small>₃</small>(H<small>₂</small>C<small>₃</small>N<small>₃</small>S<small>₃</small>)(HC<small>₃</small>N<small>₃</small>S<small>₃</small>)·H<small>₂</small>O (<strong>2</strong>), and (C<small>₂</small>N<small>₅</small>H<small>₈</small>)(H<small>₂</small>C<small>₃</small>N<small>₃</small>S<small>₃</small>)·H<small>₂</small>O (<strong>3</strong>), were successfully synthesized <em>via</em> a two-step strategy. In their anionic structures, a displaced parallel arrangement is observed among three crystals, combined with a partially distinct arbitrary intersecting arrangement. Further research findings indicate that sulfur (S) substitution (from <strong>1</strong> to <strong>2</strong>) and the optimized arrangement of functional groups (from <strong>2</strong> to <strong>3</strong>) lead to a significant enhancement in the birefringence. The experimental birefringence values at 550 nm increased from 0.259 (<strong>1</strong>) to 0.347 (<strong>2</strong>), reaching 0.403 (<strong>3</strong>). Remarkably, the birefringence performance of compound <strong>3</strong> ranks third among all reported [C<small>₃</small>N<small>₃</small>S<small>₃</small>]-based materials. Theoretical calculations reveal that its high birefringence is primarily attributed to S-substitution and the optimized arrangement of functional groups. This work provides critical guidance for further exploration of the impact of structure on birefringence performance and opens up new research directions for designing high-performance optical materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"327 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Promotion of Acetylene Semi-Hydrogenation by Oxide-Oxide Interactions in FeOX/TiO2 Catalysts","authors":"Qianjun Zhang, Yuanjing Fan, Xinhui Zhang, Fan Zhang, Yingxue Qin, Feng Feng, Jia Zhao, Chunshan Lu, Qunfeng Zhang, Qingtao Wang, Xiaonian Li","doi":"10.1039/d5qi01502b","DOIUrl":"https://doi.org/10.1039/d5qi01502b","url":null,"abstract":"Oxide catalysts have garnered significant attention in heterogeneous catalysis due to their excellent activity and cost-effectiveness. While metal-support interactions have been widely studied, the role of oxide-oxide interactions in tuning catalytic behavior remains underexplored. In this study, we developed a FeOX/TiO2 catalyst with a Fe3+/Fe2+ ratio of approximately 1:1 by depositing iron oxide onto TiO2 followed by hydrogen reduction. Compared to pure FeOX and physically mixed FeOX-TiO2, the FeOX/TiO2 catalyst demonstrated superior performance in the semi-hydrogenation of acetylene, achieving 100 % acetylene conversion and 93 % ethylene selectivity with excellent stability over 100 hours. Characterization results reveal that oxide-oxide interactions between FeOX and TiO2 significantly regulate the oxidation state of iron, promoting the formation of metastable FeOX species while inhibiting over-reduction to Fe0. In contrast, pure FeOX tends to form Fe0, which binds acetylene and ethylene too strongly, resulting in poor selectivity due to over-hydrogenation. DFT calculations show that hydrogen undergoes homolytic dissociation on pure Fe2O3 and FeOX, but heterolytic dissociation with a lower energy barrier is favored at oxygen vacancies and Fe sites on the FeOX/TiO2 interface. This facilitates the formation of active hydrogen species conducive to selective hydrogenation. Additionally, C2H4 desorption energy on FeOX/TiO2 is significantly lower than its further hydrogenatio, unlike on pure FeOX. In situ DRIFTS confirms π-bonded acetylene adsorption and the formation of OH groups during the reaction is positively correlated with the production of ethylene, verifying the critical role of H2 heterolytic dissociation. This work highlights the mechanistic importance of oxide–oxide interactions in modulating iron valence, hydrogen activation, and selectivity, offering new insights for designing high-performance oxide-based catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"107 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stabilization of Double Sandwich Structure of Mercury(II) Porphyrins: Hg•••Hg•••Hg Interactions and Structure-Function Correlation","authors":"Anindya Sarkar, Dolly Chandel, Mirza Nasib Begg, Anjani Kumar Pandey, Nityananda Dutta, Chandrani Pal, Mohammad Usman, Anindya Datta, Sankar Prasad Rath","doi":"10.1039/d5qi01593f","DOIUrl":"https://doi.org/10.1039/d5qi01593f","url":null,"abstract":"A series of stable trinuclear \"double sandwich\" complexes of mercury(II) porphyrins having linear Hg3 core have been stabilized successfully utilizing both flexible and rigid porphyrin dimer frameworks. The gross structural patterns are indeed similar: two terminal Hg(II) centers are above and below the porphyrin rings, whereas the middle Hg(II) center is sandwiched between the two rings. The mercury-nitrogen distances are largely diversified in the complexes also. Mercurophilic interactions play crucial role in stabilizing this unique structure with linear Hg•••Hg•••Hg unit overcoming the inherent instability arises out of two coplanar aromatic (porphyrin) rings placed on the exact top of each other with eclipsed conformations, a hallmark of these double sandwich complexes reported here. Interestingly, strongest mercurophilic interactions (with Hg•••Hg distances of 3.1251(11)Å and 3.1333(16)Å) are observed with highly flexible ethane-bridged porphyrin dimer. Extensive DFT calculations demonstrates that the mercurophilic interaction is evident when relativistic and dispersion effects are included and the distances are also in excellent match with the X-ray structure of the complexes. NBO and QTAIM analyses revealed distinct bond paths and bond critical points (BCPs), that are commonly recognized as key indicators of mercurophilic interactions. The absorption (with MMLCT band ~350 nm) and photoluminescent properties of the complexes display direct correlation with the strength of the Hg•••Hg interactions. Fluorescence decays at the blue end (related to the mercurophilic interactions) of the emission spectra are faster than those at the red end (associated with ligand emission) for all the complexes at both 298 K and 77 K.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A bridging thiocarbyne ligand in diiron(I) complexes enables unconventional isomerization pathways and structural diversity leading to potent cytotoxicity","authors":"Lorenzo Biancalana, Ekatarina Mihajlovic, Gianluca Ciancaleoni, Marija Mojic, Sanja Jelača, Stefano Zacchini, Guido Pampaloni, Biljana Dojčinović, Danijela Maksimovic-Ivanic, Sanja Mijatović, Fabio Marchetti","doi":"10.1039/d5qi01498k","DOIUrl":"https://doi.org/10.1039/d5qi01498k","url":null,"abstract":"Eight diiron(I) bis-cyclopentadienyl complexes with a bridging methylthiocarbyne ligand were prepared from the tris-carbonyl precursor [Fe2Cp2(CO)2(μ-CO)(μ-CSMe)]CF3SO3 (Cp = η5-C5H5) through the substitution of one or two terminal carbonyls with a variety of monodentate ligands including phosphanes/phosphite, alkyl/aryl isocyanides or iodide. All compounds were isolated in 57-84 % yield and characterized by IR and multinuclear NMR spectroscopy and by X-ray diffraction in five representative cases. Their bonding, stereochemistry and isomerization processes were investigated by NMR and DFT techniques. The water solubility and octanol-water partition coefficient heavily depend on the different monodentate ligands. All cationic complexes displayed substantial inertness in aqueous and cell culture medium solutions at 37 °C over 24-48 h. Their cytotoxicity was assessed on a panel of human cancer cell lines (HCT 116, MCF-7 and A2780) and correlates with the lipophilicity. Four compounds showed IC50 values up to the nanomolar range in colorectal, breast, and ovarian cancer cell lines. The most potent compound, [Fe2Cp2(CO)(PPh3)(μ-CO)(μ-CSMe)]CF3SO3, revealed significant disruption of cell redox homeostasis in A2780 cells, that resulted in caspase-independent apoptotic cell death. The six times higher sensitivity of A2780 cells in comparison to healthy fibroblasts (MRC-5) underlines the potential of this compound to preferably target cancer cells. Overall, the variation of monodentate ligands on a diiron(I) bis-cyclopentadienyl μ-thiocarbyne core represents a simple strategy to obtain robust compounds with tuneable physico-chemical properties and possibly also a remarkable anticancer activity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reciprocating Thermal Behavior and Thermometry Studies of Tb3+ and Gd 3+ -Oxamato Single-Ion Magnets","authors":"Cleber R Araujo Junior, Luana M Murad, Rafael V Perrella, Willian X. C. Oliveira, Carlos Basílio Pinheiro, Thais F Ramos, Patricia Patricio, Emerson F. Pedroso, Wallace C. Nunes, Pablo Rafael Trajano Ribeiro, Diego Muraca, Fernando Fabris, Marcelo Knobel, Fernando Aparecido Sigoli, Cynthia L. M. Pereira","doi":"10.1039/d5qi01603g","DOIUrl":"https://doi.org/10.1039/d5qi01603g","url":null,"abstract":"Single-ion magnets (SIMs) are prominent candidates for promoting new technologies in quantum information processing (QIP). Herein, we present two isostructural new thermostable up to ~290 <small>^o</small>C oxamato derivatives, {<em>n</em>-Bu₄N[Ln(H₂edpba)₂]}<small>_n</small> , Ln = Tb<small>³⁺</small>(<strong>1</strong>) and Gd<small>³⁺</small>(<strong>2</strong>) [H <small>₂</small>edpba<small>²</small>⁻=<em>N</em>,<em>N</em>'-<em>2</em>,2′-ethylenediphenylenebis(oxamate)]. Single-crystal X-ray diffraction reveals that <strong>1</strong>-<strong>2</strong> are one-dimensional coordination polymers with a ribbon-like structure, and metal centers are eight coordinated with a D <small>_4d</small> symmetry. Cryomagnetic studies disclose the presence of slow magnetic relaxation (SMR) behavior for <strong>1</strong> and <strong>2</strong>. For <strong>1</strong>, the Raman effect dominates the SMR at zero magnetic field, while Raman, Orbach, and reciprocating thermal behavior (RTB) mechanisms arise at higher fields. Otherwise, RTB was observed at <strong>2</strong> at low field. Solid-state photoluminescent data display a remarkable green luminescence emission, with intense and sharp bands ranging from 480 to 700 nm in the spectra, which are attributed to the <small>⁵</small> D<small>₄</small> → <small>⁷</small>F<small>_J</small> (J = 6-0) transitions of terbium(III) ions. By monitoring the temperature-dependent lifetime of the <small>⁵</small>D<small>₄</small> state following the intensity decay of the emission band attributed to the<small>⁵</small>D<small>₄</small> → <small>⁷</small> F<small>₅</small> (546 nm) transition, the complex shows a reasonable thermometric performance with a relative sensitivity of 2.77% K⁻<small>¹</small> at 448 K. <strong>1</strong> behaves as a zero-field SIM and as a photoluminescent thermometer.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anion exchange in bismuth oxyhalides for electronic property control and isolation of BiON3","authors":"Alexander E. Padilla II, Adam Jaffe","doi":"10.1039/d5qi01602a","DOIUrl":"https://doi.org/10.1039/d5qi01602a","url":null,"abstract":"Bismuth oxyhalides are a class of layered materials with rich potential for chemical and electronic tuning through anionic substitution, including the less-explored incorporation of pseudohalides such as azide (N<small>₃</small><small>⁻</small>). Here, we develop three synthetic strategies for the synthesis of BiON<small>₃</small>: post-synthetic exchange, solvothermal synthesis, and coprecipitation. We present the first structural model for BiON<small>₃</small> that is supported by Rietveld refinement, revealing a highly disordered structure that features interdigitated azide molecules between the layers. We then probe the effects of heteroanion incorporation on the electronic structure of BiON<small>₃</small>, including through the synthesis of mixed azide/iodide systems. Further, we demonstrate intriguing thermally induced reactivity in BiON<small>₃</small> that is suggestive of N atom transfer and subsequent gas evolution. This work considerably expands the available routes for synthetic control of this promising material platform.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mixed valence bimetallic Cu complexes with a urea-backboned tetradentate ligand","authors":"Anshu Singh, Samgyul Lee, Kang Mu Kwon, In Hyun Hwang, Jeongcheol Shin, Kyounghoon Lee","doi":"10.1039/d5qi01792k","DOIUrl":"https://doi.org/10.1039/d5qi01792k","url":null,"abstract":"Valence-delocalized bimetallic copper cores are found at the biological CuA sites, which are well-known for their electron transfer reactivity accompanying the transition between fully delocalized Class III and partially delocalized Class II sites. Understanding the electron transfer reactivity of CuA sites when both delocalizations are available within the same ligand platform would be helpful, but few complexes with the same ligand scaffold have been reported. Here, we report the syntheses and characterization of two different classes of bimetallic copper complexes Na(THF)x{NMe2[NNNN]Cu}2 (1) and NMe2[NNNN]Cu2(OAc) (2) using the same tetradentate ligand NMe2[NNNN]. X-ray crystallographic studies revealed that the coordination environments around bimetallic cores in 1 are distorted, whereas those for 2 are symmetric. The electron paramagnetic resonance (EPR) spectrum of 1 was deconvoluted using the different contributions from each copper, which was supported by the characteristic intervalence charge transfer (IVCT) bands of Robin-Day Class II partial delocalization observed in the UV-vis spectrum. The symmetric coordination environment of 2 matches the fully delocalized Class III copper ions, as confirmed by the characteristic septet hyperfine splitting in the EPR spectrum and IVCT band in the UV-vis spectrum. The crystallographic data and electronic spectra were successfully reproduced using the DFT and TD-DFT calculations. Frontier molecular orbital (FMO) analysis revealed that the SOMO of 1 is 3dz²-based, while that of 2 is 3dx²-y²-based. Finally, the observed structural and electronic variations of bimetallic mixed valence cores gave rise to the reactivity differences as demonstrated with tests of O2 and DPPH radical scavenging assays.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly Luminescent Divalent Tin(II) Imide Complexes [ArNSn]₂","authors":"Olga A. Kushnerova, Vasily A Ilichev, Roman V. Rumyantcev, Georgii K Fukin, Nikolay V. Somov, Wenhua Xu, Yanxia Zhao, Vladimir Alekseevich Dodonov","doi":"10.1039/d5qi01134e","DOIUrl":"https://doi.org/10.1039/d5qi01134e","url":null,"abstract":"Herein, we describe low-valent tin imides bearing a planar Sn₂N₂ core that serve as highly tunable platforms, exhibiting robust phosphorescence, redox responsiveness, and promise for advanced optoelectronic applications, including luminescent thermometry. Synthesis via transamination furnishes orange crystals of [R1,R2ArNSn]2 (R1,R2Ar = 2,6-((4-R1-С6H4)2CH)2-4-R2-C6H2) (1-4) with notably bright phosphorescence (quantum yields up to 80 % and microsecond-scale lifetimes). Temperature-dependent luminescence measurements reveal promising thermometric performance over the 298–405 K range. Detailed NMR, X-ray crystallographic, and theoretical (TD-DFT) analyses suggest a dual ligand-to-metal charge transfer and metal-centered phosphorescence mechanism, facilitated by significant spin-orbit coupling that promotes intersystem crossing to the triplet state. Notably, these complexes also undergo selective two-electron oxidation to form mixed-valence Sn(II)/Sn(IV) dimers, illustrating the antiaromatic character of the Sn₂N₂ core and its capacity for controlled redox transformations.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"60 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}