The Royal Society of Chemistry最新文献_第2页

Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines: new multidentate ligands with diverse coordination chemistry. 三（2-嘧啶基）膦和三（5-嘧啶基）膦：具有多种配位化学的新型多齿配体。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01917j

Andrey Yu Baranov, Anton V Kuzmin, Taisia S Sukhikh, Evgeny A Mostovich, Evgeny Kh Sadykov, Alexander V Artem'ev

{"title":"Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines: new multidentate ligands with diverse coordination chemistry.","authors":"Andrey Yu Baranov, Anton V Kuzmin, Taisia S Sukhikh, Evgeny A Mostovich, Evgeny Kh Sadykov, Alexander V Artem'ev","doi":"10.1039/d6dt01917j","DOIUrl":"10.1039/d6dt01917j","url":null,"abstract":"Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines, previously inaccessible multidentate ligands, have been synthesized and introduced into coordination chemistry. Theoretical studies indicate that both ligands are weak σ-donors and strong π-acceptors, exhibiting electronic properties comparable to those of trialkyl phosphites. Positional isomerism of the pyrimidyl groups induces a pronounced difference in steric profile, with the 5-isomer adopting a more open conformation and the 2-isomer a significantly more compact geometry, reflected in their Tolman cone angles of 157° and 148°, respectively. Reactions with Cu(I), Cu(II), Ag(I), Au(I), Co(II), and Pt(II) salts afforded a series of molecular complexes together with 1D and 2D coordination polymers. Tris(5-pyrimidyl)phosphine acts predominantly as a P-monodentate or P,N-/N,N'-bridging ligand, yielding extended frameworks, whereas tris(2-pyrimidyl)phosphine forms both discrete complexes and coordination polymers through P,N,N'- and P,N,N',N″-modes. Selected Cu(I) and Ag(I) complexes exhibit short-lived luminescence with emission maxima between 460 and 605 nm. These findings demonstrate the potential of symmetric tris(pyrimidyl)phosphines as versatile ligands for coordination chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14494-14506"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101068","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}

引用次数: 0

Nickel(II) coordination compounds of 4'-chloro-fenamic acid: characterization and biological activity. 4′-氯胺酸镍（II）配位化合物：表征及生物活性。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01894g

Alexandra A Galina, Georgios Malis, Anysia Zoi Damala, Konstantina C Fylaktakidou, Antonios G Hatzidimitriou, Stavros Kalogiannis, George Psomas

{"title":"Nickel(II) coordination compounds of 4'-chloro-fenamic acid: characterization and biological activity.","authors":"Alexandra A Galina, Georgios Malis, Anysia Zoi Damala, Konstantina C Fylaktakidou, Antonios G Hatzidimitriou, Stavros Kalogiannis, George Psomas","doi":"10.1039/d6dt01894g","DOIUrl":"10.1039/d6dt01894g","url":null,"abstract":"With the aim of investigating whether the coordination of fenamates to Ni(II) affects the biological profile, a chloro-derivative of fenamic acid (4'-chloro-fenamic acid) was synthesized and used as a ligand for the synthesis of seven nickel(II) complexes in the absence or presence of the nitrogen-donors pyridine, β-picoline, 1H-imidazole, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,2'-bipyridylamine. The characterization of the resultant Ni(II) complexes was performed with diverse techniques (elemental analysis, molar conductivity measurements, mass spectrometry, IR and UV-vis spectroscopy, and single-crystal X-ray crystallography). The compounds were evaluated for their in vitro biological activity in terms of the antioxidant activity via free radical scavenging and H2O2 reduction, the antimicrobial activity against two Gram-positive and two Gram-negative bacterial strains, the interaction with calf-thymus DNA, the cleavage of supercoiled pBR322 plasmid DNA (pDNA) in the dark or under UVB/UVA/visible light irradiation, and the binding affinity toward bovine and human serum albumins. The antioxidant activity of the compounds is noteworthy against 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radicals and H2O2, and comparable with that of the reference compounds. The complexes exhibit notable antimicrobial activity against the strains tested. The compounds interact with calf-thymus DNA via intercalation with binding constants of 105-106 M-1 magnitude. The pDNA-cleavage ability of the compounds is significantly enhanced under irradiation. All the compounds can bind tightly and reversibly to both albumins tested.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14582-14600"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101075","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}

引用次数: 0

Reactivity of B ← P coordinated phosphide with isocyanides: bases or nucleophiles? B←P配位磷化物与异氰酸酯的反应性：碱还是亲核试剂？

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01692h

Michal Aman, Tomáš Bíza, Libor Dostál, Zdeňka Růžičková, Emanuel Hupf, Roman Jambor

引用次数: 0

Modulating the synergistic role of device engineering in advancing lead-free perovskite solar cells. 调节器件工程在推进无铅钙钛矿太阳能电池中的协同作用。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01869f

Eman Zafar, Hamza Ali, Muhammad Abdullah Shah, Muhammad Mubeen Mudassar, Hafiz Muhammad Shrafat, Muhammad Umar Salman, Shahid M Ramay, Muhammad Asim, Shahid Atiq

{"title":"Modulating the synergistic role of device engineering in advancing lead-free perovskite solar cells.","authors":"Eman Zafar, Hamza Ali, Muhammad Abdullah Shah, Muhammad Mubeen Mudassar, Hafiz Muhammad Shrafat, Muhammad Umar Salman, Shahid M Ramay, Muhammad Asim, Shahid Atiq","doi":"10.1039/d6dt01869f","DOIUrl":"10.1039/d6dt01869f","url":null,"abstract":"In this study, a one-dimensional (1D) numerical simulation framework based on COMSOL Multiphysics was employed to investigate and optimize the structural design of a lead-free PSC. To optimize the device performance, the thickness of the ETL, absorber layer, and HTL was systematically varied, and its influence on the PV characteristics was investigated under standard operating conditions. Furthermore, the effects of operating temperature, donor concentration, and acceptor concentration on the electrical and PV behavior of the PSC were comprehensively examined. The simulation results demonstrated that the device performance was strongly influenced by both structural and material parameters. The highest PCE of approximately 19.565%, together with a Pmax value of 195.650 W m-2 and a Jsc value of 29.39 mA cm-2, was achieved at an operating temperature of 285 K when the device temperature was varied between 285 K and 325 K. In addition, the maximum FF of 88.343% and a Voc value of 1.012 V were obtained for a 50 nm-thick CsSnI3 absorber layer. These findings highlight the critical role of optimizing layer thicknesses and operating conditions in augmenting the PV performance of lead-free PSCs. Overall, the present simulation offers valuable insights into the design and optimization of environmentally benign, low-cost, and lead-free PSCs. The optimized Mg-ZnO/CsSnI3/GO device architecture demonstrates considerable potential for achieving high PV performance while addressing the toxicity concerns associated with lead-based perovskite materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14507-14520"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101033","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}

引用次数: 0

Accelerating electron transfer of NiFe-LDH via Cr-triggered electronic modulation toward a robust OER. 通过cr触发的电子调制加速NiFe-LDH的电子转移。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02110g

Duanduan Liu, Qinhua Pan, Zhongli Wu, Shuo Gao, Zhaojia He, Jiayi Wan, Changyun Chen, Zhiliang Jin, Shicheng Yan

{"title":"Accelerating electron transfer of NiFe-LDH via Cr-triggered electronic modulation toward a robust OER.","authors":"Duanduan Liu, Qinhua Pan, Zhongli Wu, Shuo Gao, Zhaojia He, Jiayi Wan, Changyun Chen, Zhiliang Jin, Shicheng Yan","doi":"10.1039/d6dt02110g","DOIUrl":"10.1039/d6dt02110g","url":null,"abstract":"The oxygen evolution reaction (OER) is a critical half-reaction in electrochemical energy conversion technology; however, its slow kinetic process limits energy conversion efficiency. Nickel iron layered double hydroxides (NiFe-LDHs) are promising OER electrocatalysts, which face challenges such as insufficient active centers and poor electron transfer ability. In this study, we report successful in situ doping of Cr ions on the surface of NiFe-LDH using a simple one-step hydrothermal method. The addition of Cr induced synergistic lattice and electronic effects, increased the active surface area and exposed more active sites, leading to excellent OER performance with a low overpotential of 219 mV at a current density of 100 mA cm-2, a Tafel slope of 58.16 mV dec-1, and long-term stability for 500 h in 1 M KOH. Cr3+ doping could adjust the coordination of Ni, Fe and O, optimize the adsorption of intermediates, accelerate electron transfer and enhance OER kinetics. This work provides a new idea for the regulation of the activity of NiFe-LDHs by heterovalent ion doping and offers a reference for low-cost and high-efficiency OER catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14563-14572"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101043","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}

引用次数: 0

An anthocyanin-curcumin colorimetric array with internal standard-guided feature switching for monitoring volatile alkaline nitrogen gases in meat freshness assessment. 一种内部标准导向特征切换的花青素-姜黄素比色阵列，用于肉类新鲜度评估中挥发性碱性氮的监测。

IF 3 3区化学

Analytical Methods Pub Date : 2026-10-20 DOI: 10.1039/d6ay01887d

Ziqin Liao, Yu Bai, Yulin Chen, Jin Shang, Wei Gan, Yuzhu Wang, Xuan Wei

{"title":"An anthocyanin-curcumin colorimetric array with internal standard-guided feature switching for monitoring volatile alkaline nitrogen gases in meat freshness assessment.","authors":"Ziqin Liao, Yu Bai, Yulin Chen, Jin Shang, Wei Gan, Yuzhu Wang, Xuan Wei","doi":"10.1039/d6ay01887d","DOIUrl":"https://doi.org/10.1039/d6ay01887d","url":null,"abstract":"Smartphone-based colorimetric sensor arrays using natural dyes are promising for on-site meat freshness assessment, but varying illumination and imaging angles compromise reliability. To address this, we developed an anthocyanin-curcumin array incorporating an α-Fe2O3 internal standard and an internal-standard-guided dynamic feature-space switching (IS-DFSS) strategy and validated its effectiveness under complex imaging conditions using ammonia as the representative analyte because it is the dominant component of total volatile basic nitrogen (TVB-N). Eight colorimetric films and the internal standard film were hydrophobically modified and assembled into a 3 × 3 array. The water contact angle increased from 63.3° to 112.9°, ensuring signal stability in high humidity. The sensing units responded strongly to TVB-N components ammonia, trimethylamine (TMA), and dimethylamine (DMA). For ammonia, Euclidean distance increased from 1.23 to 24.7 at 50 ppm and 13.7 to 65.7 at 500 ppm over 120 min, while non-alkaline volatiles (ethanol, hexanal) and non-volatile food matrix components (protein, glucose, fat) were negligible. In pork at 4 °C, array response correlated with TVB-N content (R2 = 0.987). The RGB values from 174 ammonia-responsive and 126 environment-interference images were averaged over three replicates to construct datasets, deriving HSV and Lab features. IS-DFSS with CatBoost reduced the mean absolute error to 15.85 ppm (45.46% reduction) and the mean false-signal error to 27.49 ppm (33.97% reduction) versus single RGB features, achieving R2 = 0.972. This method provides a robust, portable platform for monitoring TVB-N components, laying the foundation for reliable meat freshness assessment under complex imaging conditions.","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222891","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}

引用次数: 0

Switching of magnetic and polarization characteristics in response to intramolecular ligand-metal electron transfer in dinuclear [FeCo] compounds. 双核[FeCo]化合物中响应分子内配金属电子转移的磁性和极化特性的切换。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01478j

Serghei Ostrovsky, Sophia Klokishner

{"title":"Switching of magnetic and polarization characteristics in response to intramolecular ligand-metal electron transfer in dinuclear [FeCo] compounds.","authors":"Serghei Ostrovsky, Sophia Klokishner","doi":"10.1039/d6dt01478j","DOIUrl":"10.1039/d6dt01478j","url":null,"abstract":"A theoretical model has been developed to describe the spin transformation in the [(Fe(RR-cth))(Co(SS-cth))(μ-dhbq)](AsF6)3 compound, accompanied by a change in macroscopic polarization caused by electron density redistribution due to reversible intramolecular electron transfer between the μ-dhbq ligand and Fe ion. In this model, the states of a single complex arising from its three configurations are accounted: low-spin-Fe3+-dhbq3--low-spin-Co3+, high-spin-Fe3+-dhbq3--low-spin-Co3+ and high-spin-Fe2+-dhbq2--low-spin-Co3+. Due to the molecular structure of the compound demonstrating this transformation, the interaction between the molecular modes forming the spectrum of a single complex and the crystalline modes assuring cooperativity in the system is assumed to be responsible for the spin transformation. This model also includes the dipole-dipole interaction between complexes in the whole crystal responsible for electron density redistribution caused by electron transfer. The problem of interacting complexes is solved in the mean field approximation. On the basis of the developed model, a comprehensive explanation of the magnetic and polarization characteristics of the [(Fe(RR-cth))(Co(SS-cth))(μ-dhbq)](AsF6)3 compound is given. The inclusion of the intermediate excited configuration high-spin Fe3+-dhbq3--low-spin-Co3+, along with the ground and final configurations of the FeCo dimeric complex in the model, allows for the explanation of the unusual increase in the macroscopic polarization observed after the low-spin → high-spin transition in the iron ion is completed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14384-14393"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101052","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}

引用次数: 0

Archaeoglobus fulgidus CbiX^S is a promiscuous chelatase with a broad substrate scope. fulgidus Archaeoglobus chixs是一种杂交螯合酶，具有广泛的底物范围。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01532h

Bruce S Lickey, Matthew D Liptak

{"title":"Archaeoglobus fulgidus CbiXS is a promiscuous chelatase with a broad substrate scope.","authors":"Bruce S Lickey, Matthew D Liptak","doi":"10.1039/d6dt01532h","DOIUrl":"10.1039/d6dt01532h","url":null,"abstract":"Organisms biosynthesize square planar metal tetrapyrrole cofactors containing Mg, Fe, Co, and Ni using chelatase enzymes, which selectively insert the correct metal into a specific organic ligand. Archaeoglobus fulgidus CbiXS has been proposed to be an \"ancestral\" chelatase enzyme; in this work we have evaluated its substrate scope to ascertain whether this enzyme is a promising starting point for synthetic chelatase design. Size-exclusion chromatography revealed that CbiXS is a tetramer in solution regardless of the metalation state of the enzyme, in contrast to the dimeric structure of the nickel chelatase CfbA. Reaction conditions that minimize enzyme-free metal insertion into tetrapyrroles were determined, which revealed that many of the in vitro activity assays reported in the literature for chelatase enzymes may be plagued by non-enzymatic metal insertion. Under these conditions that minimize uncatalyzed metal insertion, CbiXS was observed to catalyze metal insertion for six different combinations of metal and tetrapyrrole. Based upon the turnover numbers of these reactions, CbiXS is most effective at catalyzing metal insertion for reactants similar to its native substrates: cobalt and sirohydrochlorin. Kinetic analysis for reactions with varying substrate concentrations revealed that CbiXS may be substrate-inhibited for non-native substrates. In addition, the kinetic data identifies metal-ligand bond formation as the rate-limiting step of the enzyme. Due to its broad substrate scope, CbiXS is an encouraging starting point for synthetic chelatase design that could yield non-natural metal tetrapyrroles for use in the biotechnology sector.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14614-14624"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101105","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}

引用次数: 0

Mechanism of the dehydrogenation of Mg(BH₄)₂·THF_0.25 to Mg(B₁₀H₁₀): role of the THF solvate. Mg(BH4)2·THF0.25脱氢生成Mg（B10H10）的机理：THF溶剂的作用

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02098d

McKinley A Prager, Sunil Shrestha, Phuong Q H Nyugen, Natalie McNurlin, Stephen Kim, Craig M Jensen

{"title":"Mechanism of the dehydrogenation of Mg(BH4)2·THF0.25 to Mg(B10H10): role of the THF solvate.","authors":"McKinley A Prager, Sunil Shrestha, Phuong Q H Nyugen, Natalie McNurlin, Stephen Kim, Craig M Jensen","doi":"10.1039/d6dt02098d","DOIUrl":"10.1039/d6dt02098d","url":null,"abstract":"Dehydrogenation of Mg(BH4)2·THFx (1·THF) at 180 °C has been previously found to produce primarily a mixture of Mg(B3H8)2 (2) and Mg(B10H10) (3). It has now been found that dehydrogenation under a H2 back pressure of 20 bar suppresses the formation of 2 and results in very high (>95%) selectivity for 3. The production of 3 is not inhibited by hydrogen pressure. This demonstrates that the reaction pathway leading to its formation does not involve reversible, rate limiting H2 elimination and is divergent from the pathway leading to 2. Unlike the pathway leading to the formation of 2, the dehydrogenation of 1·THF to 3 is irreversible under moderate conditions. Concurrent with the dehydrogenation reaction, THF is slowly converted to Mg(OBun)2, curtailing the production 3. However, the dehydrogenation process is revived by addition of a fresh aloquate of THF to the reaction mixtures. It is hypothesized that THF enables the production of 3 by stabilizing the key intermediate, [B2H5]- and by the low melting point (<100 °C) of 1·THF which allows long-range diffusion of borane anions at much lower energies than those required for their transport in the solid-state.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14521-14525"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101060","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}

引用次数: 0

A non-resonant Kβ valence-to-core X-ray emission approach for fluorine and oxygen differentiation in Zr compounds. Zr化合物中氟和氧分化的非共振Kβ价核x射线发射方法。

IF 3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-20 DOI: 10.1039/d6cp01440b

Christian Heinekamp, C Tufan Cakir, Ana Guilherme Buzanich, Konstantin Klementiev, Michael Roemelt, Thomas Braun, Franziska Emmerling

{"title":"A non-resonant Kβ valence-to-core X-ray emission approach for fluorine and oxygen differentiation in Zr compounds.","authors":"Christian Heinekamp, C Tufan Cakir, Ana Guilherme Buzanich, Konstantin Klementiev, Michael Roemelt, Thomas Braun, Franziska Emmerling","doi":"10.1039/d6cp01440b","DOIUrl":"https://doi.org/10.1039/d6cp01440b","url":null,"abstract":"Valence-to-core (VtC) X-ray emission spectroscopy (XES) is a powerful probe for the local electronic structure in transition-metal materials, but its potential for 4d metals such as zirconium remains largely unexplored. Here, we demonstrate that non-resonant Zr Kβ VtC XES provides quantitative descriptors that are sensitive to ligand chemistry, by probing fluorine- and oxygen-based coordination environments in well-defined and catalytically relevant Zr compounds. High-resolution X-ray emission spectra containing Zr-Kβ2 and -Kβ4 are recorded for a series of reference systems (ZrO2, ZrF4, ZrF4·H2O, ZrCl4, Zr(acac)4, Zr metal) and for Zr fluoride materials, and are analysed using quantitative line-shape parameters. Projected densities of states (PDOS) obtained from FDMNES calculations reveal that fluorine coordination enhances the Kβ″ contribution and induces characteristic changes in Kβ2 intensity and asymmetry compared to oxygen and chlorine ligands. These ligand-specific spectral signatures enable a systematic discrimination between F- and O-containing coordination spheres, even when conventional X-ray absorption or diffraction techniques provide limited contrast. This combined experimental-computational framework demonstrates that Zr Kβ VtC XES can resolve subtle ligand-dependent coordination changes in Zr-based materials, offering a general route to identify active structures in C-F bond activation and oxygen-evolution catalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222889","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}

引用次数: 0