European Journal of Inorganic Chemistry最新文献

{"title":"A Novel Ternary Composite of GO/NiCoFe2O4/MIL-53 for Enhanced Copper Removal from Wastewater","authors":"Eman A. Elmenofy,&nbsp;Omnia I. Ali,&nbsp;A. T. Kandil,&nbsp;Sheta M. Sheta,&nbsp;Said M. El-sheikh","doi":"10.1002/ejic.202400795","DOIUrl":"https://doi.org/10.1002/ejic.202400795","url":null,"abstract":"<p>Excess copper levels have been associated with Alzheimer's disease, aging, mental illness, and DNA damage. As a result, the copper ions’ removal from water resources has become a major challenge. In this study, a novel ternary GO/NiCoFe₂O₄/MIL-53 composite was synthesized for the first time based upon a combination of GO, NiCoFe₂O₄, and MIL-53(Al) MOF, which effectively removed Cu²⁺ ions from aqueous solutions. The characterization was utilizing XRD, SEM/EDX, TEM, FT-IR, TGA, XPS, and BET analysis. XRD and FT-IR confirmed the formation of the GO/NiCoFe₂O₄/MIL-53 composite and Cu²⁺ adsorption. SEM images showed that MIL-53-MOF crystals have a rhombohedral crystal structure, while the NiCoFe₂O₄ particles have spindle-like crystals organized in flower-like shapes. The prepared GO/NiCoFe₂O₄/MIL-53 composite had a high specific surface area of 1235.58 m² g⁻¹ and exhibited characteristics of a mesoporous structure. The GO/NiCoFe₂O₄/MIL-53 composite showed high Cu²⁺ adsorption capacity of 90.09 mg g⁻¹ and reserved high removal ability even after five cycles. Different experimental factors like pH, initial-concentration, temperature, contact-time, ionic-strength, composite dosage, and coexisting-ions, were explored. The results showed that Cu²⁺ removal was fast and effective, with an efficiency exceeding 80 % within 30 minutes. The process of Cu²⁺ adsorption on the composite was exothermic, spontaneous, and followed the pseudo-second-order kinetics and Langmuir isothermal model. The Cu²⁺ recovery from water samples ranged between 86.5 %–94.3 %, indicating the excellent efficiency of the GO/NiCoFe₂O₄/MIL-53 composite for copper removal from real samples. Furthermore, the GO/NiCoFe₂O₄/MIL-53 composite established the best performance compared to other works for copper removal from wastewater.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741013","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: 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":"ETS-NOCV Analysis of σ-Donation and π-Backdonation in Complexes of Boron Based Lewis Acids with N2, CO and NH3","authors":"Tore Brinck,&nbsp;Filip Sagan,&nbsp;Mariusz Mitoraj","doi":"10.1002/ejic.202400845","DOIUrl":"https://doi.org/10.1002/ejic.202400845","url":null,"abstract":"<p>Lewis acids B(SiR₃)₃ and B(GeR₃)₃ form anomalously strong complexes with Lewis bases N₂ and CO. Intramolecular B−N/C bonds are generally in the range 1.45–1.50 Å and shorter than the sum of B and N/C covalent radii. Bonding analyses have shown that the strong bonds are a consequence of a novel σ-donation and π-backdonation mechanism, where electrons are donated into an empty <i>sp</i>^<i>3</i>-type orbital on B (LUMO) from the σ-orbitals of N₂/CO and electrons are backdonated from the B−Si/Ge σ-bonds into the π-type orbitals of N₂/CO. Here we have analyzed the complexes between Lewis acids B(SiH₃)₃ and B(CF₃)₃ and Lewis bases N₂, CO and NH₃ using the <i>extended transition state – natural orbitals for chemical valence</i> (ETS-NOCV) method. Both σ-donation and π-backdonation are present in all complexes, and deformation densities due to the two mechanisms, i. e. NOCV pair densities, are surprisingly similar in character. Energy stabilization due to π-backdonation is much larger for the complexes of B(SiH₃)₃ with N₂ and CO, and σ-donation stabilization is also enhanced compared to the corresponding complexes of B(CF₃)₃. Differential electrostatic potential indicate that the enhanced stabilization of the B(SiH₃)₃ complexes is largely an effect of reduced charge separation due to the balance between σ-donation and π-backdonation.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 12","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.202400845","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861627","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":"Axial Ligand Lability and Coordination Induced Spin State Variations of Tetracarbene Iron(II) Thiolato Complexes","authors":"Isabelle Becker,&nbsp;Massimiliano Morganti,&nbsp;Sophie Jana Gross,&nbsp;Serhiy Demeshko,&nbsp;Sebastian Dechert,&nbsp;Michael John,&nbsp;Franc Meyer","doi":"10.1002/ejic.202400823","DOIUrl":"https://doi.org/10.1002/ejic.202400823","url":null,"abstract":"<p>Starting from the six-coordinate tetracarbene iron(II) bis(acetonitrile) complexes, a series of structurally characterized iron(II) thiolato complexes [(MTC)Fe^II(SR)(NCMe)]OTf (R=^<i>t</i>Bu, Ada) was synthesized based on the equatorial macrocyclic tetracarbene (MTC) ligands ^18HL (3,9,14,20-tetraaza-1,6,12,17-tetraazoniapenta-cyclohex-acosane-1(23),4,6(26),10,12(25),15,17(24),21-octaene) and its octamethylated derivative ^18MeL. Those thiolato complexes can be viewed as bioinspired organometallic analogues of the iron(II) state of heme enzymes with axial cysteine coordination like cytochrome P450. Depending on the equatorial and axial ligands, the spin states of the complexes can change from low-spin (<i>S</i>=0) to intermediate-spin (<i>S</i>=1), but the strong donation by the MTC prevents the formation of any high-spin species. The electronic structure was analyzed using ⁵⁷Fe Mössbauer spectroscopy and magnetic susceptibility measurements. In addition, both axial ligands – acetonitrile and the thiolate – were found to be labile, leading to scrambling in solution as observed <i>via</i> NMR spectroscopy and ESI-MS. A temperature-dependent equilibrium was found for all complexes due to dissociation of the axial MeCN forming a 5-coordinate species in solution. This 5-coordinate species is significantly preferred for the ^18MeL being in line with the higher donating ability of the equatorial ligand and thus the weakening of the axial ligand bonds, in line with cyclic voltammetry data.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 11","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.202400823","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822276","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":"A N3-geminal Al/P-Based Intramolecular Lewis Pair: Synthesis, Characterization and Reactivity","authors":"Xiong Sun,&nbsp;Zhuoyi Xie,&nbsp;Lianghua Zou","doi":"10.1002/ejic.202400842","DOIUrl":"https://doi.org/10.1002/ejic.202400842","url":null,"abstract":"<p>Frustrated Lewis pairs (FLPs) play a crucial role in main-group chemistry due to the diverse reactivities towards small molecules and extensive applications in organic transformations. The intramolecular FLP systems known in the literature are mainly consisted of boron-containing Lewis acids and the linkers are almost exclusively based on carbon. Herein, the nitrogen-linked geminal Al/P Lewis pair <b>1</b> was readily prepared by salt metathesis reaction between AlBr₃ and N[CH₂CH₂NLi-PtBu₂]₃ in toluene at room temperature. Further studies confirmed that <b>1</b> exhibited typical FLP-type reactivity towards heterocumulenes, isocyanide and transition metal precursors. Single-crystal X-ray diffraction analysis revealed that all the addition products contained a penta-coordinated aluminum atom which was less common in FLP chemistry. This study demonstrated that the resulting Al/P-based system represented an efficient alternative class of FLPs and enriched the linker motifs of intramolecular FLPs.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 11","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822277","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}