European Journal of Inorganic Chemistry最新文献

{"title":"Front Cover: Rare Earth Acylpyrazolonates-Synthesis, Structure, Luminescent Properties and Applications (Eur. J. Inorg. Chem. 6/2025)","authors":"Yuriy A. Belousov,&nbsp;Andrei A. Drozdov,&nbsp;Daniil D. Shikin,&nbsp;Alessia Tombesi,&nbsp;Riccardo Pettinari,&nbsp;Fabio Marchetti,&nbsp;Claudio Pettinari","doi":"10.1002/ejic.202580601","DOIUrl":"https://doi.org/10.1002/ejic.202580601","url":null,"abstract":"<p><b>The Front Cover</b> shows that rare-earth acylpyrazolonate complexes can be used in several applications, from the creation of luminescent materials, such as the development of emitting and auxiliary layers in OLED devices, to magnetic materials. The electronic and structural properties of the ligands suggest that the donors are effective sensitizers of various lanthanides emitting in the visible and IR region. More information can be found in the Review by C. Pettinari and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 6","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202580601","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning the Ligand Properties of PNacPNac Stabilized Group 13 Carbenoids Towards Small Molecule Activation: A Theoretical Study","authors":"Sahtaz Ahmed,&nbsp;Deeptangshu Sarkar,&nbsp;Ashwini K. Phukan","doi":"10.1002/ejic.202400798","DOIUrl":"https://doi.org/10.1002/ejic.202400798","url":null,"abstract":"<p>Quantum chemical calculations have been carried out to design skeletally substituted PNacPNac stabilized Al(I)/Ga(I) carbenoids to probe their ligand properties and reactivity towards the activation of small molecules like NH₃, PH₃ and H₂. All the proposed systems are found to have a considerably stable singlet ground state. The activation barriers associated with the cleavage of N−H, P−H and H−H bonds for all the proposed PNacPNac stabilized Al(I)/Ga(I) systems are found to be either lower or comparable to that of the experimentally evaluated systems.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing the Electrochemical Performance of Nickel-Rich Layered Cathode Material (NMC 622) for Lithium-Ion Batteries by Ultrathin Conductive Ceria-Surface Coating","authors":"Itumeleng Seotsanyana-Mokhosi,&nbsp;Kenneth I. Ozoemena","doi":"10.1002/ejic.202400689","DOIUrl":"https://doi.org/10.1002/ejic.202400689","url":null,"abstract":"<p>Layered LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) has been lauded as robust and fitting candidates for the development of the next generation lithium-ion batteries for electric vehicles and other high energy demanding applications. However, widespread commercialization of NMC622 cathode material has been frustrated by its poor cycling performance which is due to structural instability. This work shows that the electrochemical performance of the NMC622 can be greatly enhanced by surface-coating with CeO₂. A commercial NMC622 is chemically modified with a very low amount of CeO₂ (~2 %) to form an ultrathin CeO₂-coated NMC622 surface (NMC622-c). The coated electrode material exhibits enhanced electrochemical performance compared to its pristine counterpart, especially in terms of Li-ion diffusion kinetics and capacity retention. This enhancement has been made possible by the NMC622-c overcoming the destructive H2/H3 phase transition, reduced Ni/Li mixing, and improved ordered hexagonal structure. Improved Li diffusion rate has also been improved for long battery life. This work provides excellent insight to researchers and entrepreneurs working hard to overcome the inherent challenges of the NMC622 and related NMC layered cathode materials.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400689","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rhodacycles Activity in P-Directed Rhodium-Catalyzed Synthesis of π-Extended Aromatic Fluoranthenyl Phosphines","authors":"Charline Sire,&nbsp;Anthonia Tsivery,&nbsp;Henri Sabbadin,&nbsp;Dr. Hélène Cattey,&nbsp;Marie-José Penouilh,&nbsp;Prof. Dr. Paul Fleurat-Lessard,&nbsp;Prof. Dr. Jean-Cyrille Hierso,&nbsp;Dr. Julien Roger","doi":"10.1002/ejic.202400721","DOIUrl":"https://doi.org/10.1002/ejic.202400721","url":null,"abstract":"<p>We report herein novel polyarylated diphenylphosphino-1-fluoranthenyl ligands by rhodium-catalyzed phosphine-directed C−H arylation. The nature of the rhodium precatalysts that is employed plays an essential role for the control of the reaction and its resulting product. By using the dimeric [Rh^(III)Cl₂Cp*]₂ as the catalyst, a “classical” single <i>peri</i>-functionalization of the polycyclic aromatic hydrocarbons phosphine selectively occurs. Conversely, the use of the ionic [Rh^(I)(COD)₂] BF₄ as the catalyst reveals an unexpected post-rearrangement that is characterized by the migration of the directing phosphino-group on the inserted aryl moiety. In this process, a concurrent cascade extension of the functionalization is also achieved by the introduction of a second aryl moiety. We focused our attention on the rhodium catalytic species formed, and the five or seven-membered rhodacycles as intermediates involved in these C−H catalytic cascade processes. Besides the electronic effects attached to Rh(I) and Rh(III) precatalysts, either cationic or neutral, our results clearly suggest the role of the pentamethylcyclopentadienyl substituent in the selectivity of <i>peri</i>-C−H-arylation. Conversely, rhodium stabilized by weakly bonded more fluxional bis-cyclooctadienyl ligands enters more easily into further reactivity, promoting 2-fold arylation reactions or even participate to diphenylphosphino group rearrangement.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400721","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile Synthesis of Hierarchical Sn-Beta Zeolite by Tuning Chemical Equilibrium of Fluoride Etching","authors":"Ruxing Zhao,&nbsp;Qingrun Meng,&nbsp;Guanchao Wang,&nbsp;Xu Feng,&nbsp;Dongchen Shi","doi":"10.1002/ejic.202400692","DOIUrl":"https://doi.org/10.1002/ejic.202400692","url":null,"abstract":"<p>The Sn-Beta zeolite is commonly known as a unique Lewis acid catalyst, however, usually suffers from the drawback of diffusion limitation within zeolitic micropores. To address these issues, the present work reports a facile fluoride etching approach for the synthesis of hierarchical Sn-Beta zeolites by tuning chemical equilibrium of HF and NH₄F mixed solutions. It was found that the etching of HF solution alone only extracts Sn species in the Sn-Beta framework while adding NH₄F into HF solution shifts the chemical equilibria to produce more reactive HF₂ ⁻ for Si, thereby achieving unbiases selective extraction of Si and Sn from *BEA framework. The obtained hierarchical Sn-Beta zeolite possessed excellent catalytic activity in Baeyer-Villiger oxidation of bulky 2-adamantanone with aqueous hydrogen peroxide. Structure-performance relationship revealed that the Lewis acid site and the pore structure are two crucial factors determining the catalytic activity. The former was identified as a catalytic active center while the latter increase the accessibility to active sites in microporous Sn-Beta zeolites by forming hierarchical porosity. Therefore, the sample obtained after optimizing the conditions of NH₄F- HF mixed solutions presented a remarkably enhanced catalytic oxidation activity for bulky molecules.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conformational Flexibility-Triggered Differential Sensing and Metric for the Naturally Abundant Transition Metal Ions by a Pyrrole-Functional Schiff Base","authors":"Nabanita Deb,&nbsp;Chitra Thottingal Jayaprakasan,&nbsp;Gembali Raju,&nbsp;Vaibhav Singh,&nbsp;Arun Kumar Bar","doi":"10.1002/ejic.202400799","DOIUrl":"https://doi.org/10.1002/ejic.202400799","url":null,"abstract":"<p>A hitherto unknown Schiff base ligand (<b>H₃L</b>) is synthesized upon condensing benzhydrazide with 2,5-diformylpyrrole in 2 : 1 molar ratio. <b>H₃L</b> displays well-resolved UV-vis absorption bands with high molar extinction coefficients. It also exhibits photoluminescence (PL) with large Stokes shifts and high emission intensities. <b>H₃L</b> is found to be a remarkable chemosensor for commonly abundant transition metal ions through its UV-vis and photoluminiscence (PL) spectral change. It can not only detect and quantify various transition metal ions but can also distinguish them from their mixtures under restricted circumstances. Detailed computational analyses revealed that such a unique photophysical characteristic originates from ligand-centric internal electronic state rearrangement. <b>H₃L</b> can switch among an enormously large number of low-energy-barrier conformers in its free state. The degree of π-electron conjugation across the molecular skeleton of <b>H₃L</b> is dictated by its conformation. Its UV-vis/PL spectral signature is subject to an analyte metal ion. Treatment of <b>H₃L</b> with a transition metal ion leads to the formation of [2+2] self-assembled discrete coordination complex, which renders the restriction on the conformational freedom of <b>H₃L</b>. The commonly abundant alkali/alkaline earth metal ions and commonly abundant anions are found to cause <i>no-to-negligible</i> interference. The chemosensing is affirmed to occur practically instantaneously with excellent limit of detection.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photocatalytic Nitrogen Fixation Materials and Mechanistic Features: State of the Art and Future Perspectives","authors":"Costanza Tedesco,&nbsp;Giulia Giovilli,&nbsp;Lorenzo Malavasi","doi":"10.1002/ejic.202400686","DOIUrl":"https://doi.org/10.1002/ejic.202400686","url":null,"abstract":"<p>photocatalysis, nitrogen photofixation, material chemistry, heterojunctionThe essential role ammonia occupies, considering both its major industrial use for nitrogen-rich fertilizers and the possibility of being utilized as medium for energy storage, clashes with the environmental drawbacks of the Haber-Bosch process, its main production method. This review investigates the potential of photocatalytic nitrogen fixation (PNF) as an eco-friendly approach, driven by solar energy and inspired by natural nitrogenase enzymes. It traces the historical development of nitrogen fixation methods and focuses on recent advancements in photocatalytic materials, including metal oxides, sulfides, and composite systems. Strategies to enhance catalytic performance – including doping, defect engineering, and heterojunction construction – are showcased, thus providing a way to mitigate low conversion efficiency and electron-hole recombination. The work concludes by presenting emergent materials that could revolutionize the field, offering new paths for sustainable ammonia production.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400686","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Instigating Visible Light Inspired DNA Impairment by ROS Harvesting Ir(III)-Cyclometallated Imidazophenanthroline Complexes Against MDA-MB-231 Cells","authors":"Sreejani Ghosh,&nbsp;Priyankar Paira","doi":"10.1002/ejic.202400769","DOIUrl":"https://doi.org/10.1002/ejic.202400769","url":null,"abstract":"<p>Difficulties to abate the vehemence of deleterious triple-negative breast cancer (TNBC) is an ardent issue in the current context of anticancer research due to the lack of a selective treatment modality. To address this issue, herein we have endeavored to establish the imidazophenanthroline-based Ir(III)-cyclometallated heteroleptic complexes, suited for the one-photon photodynamic therapy (OP-PDT) under irradiation of visible light (400–700 nm) possessing long-lived excited triplet state and significant photostability. Among three synthesized complexes, [<b>L1Ir</b>], [<b>L2Ir</b>], [<b>L3Ir</b>], the complex [<b>L2Ir</b>] has been recognized as the most competent complex to exhibit selective phototoxicity (IC₅₀=3.8 <i>μ</i>M; PI^c=78.94) in MDA-MB-231 triple-negative breast cancer cells. The significant phototoxicity of the complexes has arisen due to the production of reactive singlet oxygen (¹O₂) following the type-II pathway (Φ_s=0.26). Also, the complexes have shown the proficiency in oxidation of reduced nicotinamide adenine dinucleotide (NADH) (TOF=37.82 h⁻¹) indicating the possibility of reactive oxygen species (O₂⋅⁻, ⋅OH) generation through type-I pathway upon visible light irradiation. Along with this, intracellular glutathione (GSH) depletion capabilities have endued the complexes to unarm the TNBC cells in front of the profuse amount of ROS instigating the programmed cell death (PCD) through substantial DNA damage.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Front Cover: (Eur. J. Inorg. Chem. 5/2025)","authors":"","doi":"10.1002/ejic.202580501","DOIUrl":"https://doi.org/10.1002/ejic.202580501","url":null,"abstract":"<p>\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 5","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202580501","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CuII and ZnII Complexes with 1,3,4-Thiadiazole-5-Thiomethyl-Based Diamide","authors":"Ana Júlia Zimmermann Londero,&nbsp;Ulrich Abram,&nbsp;Maximilian Roca Jungfer,&nbsp;Prof. Vânia Denise Schwade","doi":"10.1002/ejic.202400736","DOIUrl":"https://doi.org/10.1002/ejic.202400736","url":null,"abstract":"<p>The diamide ligand, <i>N</i>,<i>N’</i>-bis(5-thiomethyl-1,3,4-thiadiazol-2-yl)-2,6-pyridinedicarboxamide (<b>H₂L</b>) in its solvate form has two planar acetylamino groups, which are twisted slightly from the plane of the 5-thiomethyl-thiadiazole rings. The ligand reacts with: (i) copper(II) salts forming binuclear and pentanuclear compounds; (ii) zinc(II) acetate leading to an anionic trinuclear complex. The molecular structures of [Cu₂(μ-H₂O)(L)₂] (<b>1</b>), [Cu₅(dmf)(μ₃-OH)₂(L)₃(L^b)]_0.8[Cu₅(μ₃-OH)₂(L)₃(L^b)]_0.2 ⋅ 0.5DMF⋅H₂O (<b>2</b>) and [Zn(H₂O)₂(dmf)₄][Zn₃(μ₃-OH)(L)₃]₂ ⋅ 2DMF ⋅ H₂O (<b>3</b>) (where {L^b}²⁻ represents the partially hydrolyzed ligand) were confirmed by X-ray diffractometry. We have found that compound <b>1</b> can exist as two tautomers: the aqua bridge in [Cu₂(μ-H₂O)(L)₂] and the hydroxy bridge in [Cu₂(μ-OH)(HL)(L)]. All compounds were characterized by elemental analysis and ESI mass spectrometry as well as FT-IR, Raman and UV-Vis spectroscopy. The luminescence properties of H₂L⋅DMF and compound <b>3</b> were investigated. Compound <b>3</b> has strong fluorescence with the emission band centered at 508 nm, and fluorescence lifetime of 1.44 ns. The potential of chalcogen bonding interactions in aroylamidothiadiazoles and their compounds is discussed based on DFT calculations. The <i>cis</i>-ketone-configuration of oxygen and sulfur is energetically favored over other potential rota- and tautomers. Most importantly, the deprotonation of the ligand increases the O ⋅ ⋅ ⋅ S interaction strength due to a larger negative charge at oxygen leading to increased conformational stability in the coordination compounds. A massively increased delocalization of the nitrogen atoms lone pair in the deprotonated state compared to the protonated state, however, may be the main reason for the observed conformation.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}