European Journal of Inorganic Chemistry最新文献

{"title":"Extraction of 244Cm Using 3,3′-Dibutyloxyphenyl-bis-1,2,4-Triazinyl-2,6-Pyridine as a Bipolar Complexant: A Fundamental, density functional theory, and Spectroscopic Study","authors":"Jessica A. Jackson,&nbsp;Lesta S. Fletcher,&nbsp;Allison A. Peroutka,&nbsp;Samiat O. Olayiwola,&nbsp;Nickolas A. Joyner,&nbsp;Jenifer C. Shafer,&nbsp;David A. Dixon,&nbsp;Jesse D. Carrick","doi":"10.1002/ejic.202400818","DOIUrl":"https://doi.org/10.1002/ejic.202400818","url":null,"abstract":"<p>Defining effective separation processes to extract the minor actinides from lanthanides remains a significant challenge in the expansion of nuclear power as a greener alternative to carbon-based energy. Minor actinides, Am, Cm, and Np, are routinely produced as byproducts of nuclear fission and present numerous challenges for separation from the neutron-poisoning lanthanides, including similar oxidation states, cationic radii, and coordination number. Transmutation of the minor actinides to fast-neutron reactors to decrease the radiotoxicity and volume of high-level waste stored in a geologic repository necessarily demands chemoselective isolation strategies. In this work, a comprehensive biphasic extraction, theoretical, and spectroscopic study using the recently discovered soft-N-donor, bipolar complexant, 3,3′-dibutyloxy-phenyl-bis-[1,2,4]-triazinyl-2,6,-pyridine (BOB-BTP) for ²⁴⁴Cm³⁺ extraction is described. Solvent extraction, density functional theory, and spectroscopic data are reported herein.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 18","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472892","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: Stabilities and Limitations in the Reactivity of Phosphorus Ylide-Based Aluminum– and Gallium–Carbon Ambiphiles: A Combined Experimental and Computational Approach (Eur. J. Inorg. Chem. 16/2025)","authors":"Felix Krämer,&nbsp;Pascal Weisenburger,&nbsp;Israel Fernández,&nbsp;Frank Breher","doi":"10.1002/ejic.202581601","DOIUrl":"https://doi.org/10.1002/ejic.202581601","url":null,"abstract":"<p><b>The Front Cover</b> shows a sketchpad with the structure of the formal methanol activation product of an aluminum–carbon-based ambiphile that is formed by the elimination of ammonia. A water molecule is shown above the eliminated ammonia molecule, indicating that replacement by water can also be realized. On the left, other small molecules that do not react with the title compounds are shown. The product of trimerization of phenyl isocyanate, for which the ambiphiles act as catalysts, is shown on the left. To the right are shown the insertion products of carbon dioxide and acetonitrile. The ticked reaction product with carbon dioxide can be realized, the crossed-out acetonitrile product cannot. The reaction path bottom right shows that the insertion process of acetonitrile is endergonic overall and rather high activation barriers are predicted. More information can be found in the Research Article by I. Fernández, F. Breher and co-workers (DOI: 10.1002/ejic.202500165).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 16","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202581601","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144220126","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":"A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO-66","authors":"Francesco Della Croce,&nbsp;Matthew J. McPherson,&nbsp;Elena Pulidori,&nbsp;Celia Duce,&nbsp;Marco Taddei","doi":"10.1002/ejic.202500110","DOIUrl":"https://doi.org/10.1002/ejic.202500110","url":null,"abstract":"<p>Aliphatic amine-functionalized metal–organic frameworks (MOFs) are receiving increasing attention for their potential as adsorbents for CO₂. In this work, a two-step postsynthetic approach is presented, applied to defective Zr^IV-based MOF UiO-66, which involves the exchange of <i>N</i>-tert-butyloxycarbonyl (Boc) protected ω-amino acids for defect-compensating formate groups, followed by thermal deprotection of the Boc groups to yield free amine groups. The chosen amino acids are glycine, 3-aminopropionic acid (β-alanine), γ-aminobutyric acid, and 5-aminovaleric acid. Postsynthetic exchange of the Boc-protected amino acids is carried out in <i>N</i>,<i>N</i>-dimethylformamide, observing no structural damage and a dependence of the loading of functional groups on the length of the aliphatic chain (the longer the chain, the lower the loading). Deprotection is achieved by heating the solids to 160 °C under a N₂ stream, accompanied by the release of CO₂ and isobutylene, as confirmed by thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry. The deprotected MOFs are characterized by their gas sorption properties, finding that functionalization of the defects led to a predictable decrease in porosity, without enhancing the affinity for CO₂, suggesting that the amine groups might not be accessible.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614897","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":"Structure-Activity Relationship of Metal-Organic Frameworks-Derived Ni–Al Catalysts for CO Methanation Under Pyrolysis Strategy","authors":"Junxia Wu,&nbsp;Ertong Zhang,&nbsp;Chunjie Han,&nbsp;Bin Li,&nbsp;Xianjun Zhang,&nbsp;Hongwei Wang,&nbsp;Hong Wang","doi":"10.1002/ejic.202500129","DOIUrl":"https://doi.org/10.1002/ejic.202500129","url":null,"abstract":"<p>The conversion of metal-organic frameworks (MOFs) to MOF-derived composites via pyrolysis strategies can effectively address the shortcomings of MOFs, such as the small number of catalytic active sites and poor chemical stability, which limit practical catalytic applications. This article presents a series of Ni/MOF-derived composite materials with distinct morphologies, obtained by varying the calcination temperature. The NiO/M-Al 900 catalysts, calcined at 900 °C, form a NiO structure supported by NiAl₂O₄, which enhances the Ni–Al interaction. This catalyst inherits the high specific surface area (143.23 m² g⁻¹) and rich pore structure of the MOF, resulting in superior catalytic performance with CO conversion and CH₄ selectivity reaching 100% and 67%, respectively, and maintaining high activity under a 90 h stability test. The optimal Ni–Al interaction and the synergistic effect of the porous structure improve the dispersion and utilization of the active components, preventing sintering and carbon deposition of the catalysts during the reaction. This discovery provides a novel approach to designing high-performance multiphase MOF-derived composites for practical catalytic processes.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614898","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":"Phosphine-Ligated Cobalt(II) Acetylacetonate Complexes","authors":"J. P. I. Dulmini Jayawardhena,&nbsp;Jeanette A. Krause,&nbsp;Hairong Guan","doi":"10.1002/ejic.202500157","DOIUrl":"https://doi.org/10.1002/ejic.202500157","url":null,"abstract":"<p>Cobalt(II) acetylacetonate complexes bearing a phosphine ligand can be key intermediates or precursors to cobalt-based catalysts; however, they have been rarely studied, especially from a molecular structure point of view. This work is focused on the understanding of how different phosphines react with Co(acac)₂ (acac = acetylacetonate). To do so, a variety of analytical tools, including NMR and IR spectroscopy, X-ray crystallography, mass spectrometry, and elemental analysis, have been used to study the reactions and characterize the isolated products. These results have shown that the monodentate ligand, HPPh₂, binds to Co(acac)₂ weakly and reversibly to produce Co₂(acac)₄(HPPh₂), whereas the bidentate ligand, 1,2-bis(diphenylphosphino)ethane (dppe), interacts with Co(acac)₂ more strongly to yield a 1D coordination polymer of Co(acac)₂(dppe). 2-(Dicyclohexylphosphino)methyl-1 H-pyrrole (^CyPN^H), which is a pyrrole-tethered phosphine, forms an unusual 5-coordinate cobalt complex, Co(acac)₂(^CyPN^H), in which the pyrrole moiety participates in a bifurcated hydrogen–bonding interaction with the [acac]^– ligands. In contrast, another bidentate ligand, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), fails to react with Co(acac)₂, presumably due to its wide bite angle and difficulty in bridging two metals.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500157","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615382","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":"Front Cover: Theoretical Study of Local Environmental Effect on Electronic Structure of M-Cluster (Eur. J. Inorg. Chem. 15/2025)","authors":"Kazuki Honjo,&nbsp;Taigo Kamimura,&nbsp;Kohei Tada,&nbsp;Ryohei Kishi,&nbsp;Yasutaka Kitagawa","doi":"10.1002/ejic.202581501","DOIUrl":"https://doi.org/10.1002/ejic.202581501","url":null,"abstract":"<p><b>The Front Cover</b> shows a local environmental effect on the electronic structure of the M-cluster of nitrogenase, which was examined by DFT calculations from the viewpoint of the hydrogen bonds and water molecules. Hydrogen bonds from Ser265 significantly contribute to the stability of the LUMO, while the water molecules around the HCA strongly stabilize the HOMO. The contribution of Ser265 is, however, suppressed when an outer environmental field is applied. The results provide suggestions for the ligand design of synthesized FeS clusters. More information can be found in the Research Article by Y. Kitagawa and co-workers (DOI: 10.1002/ejic.202500016).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 15","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202581501","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144171340","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":"Structural and Kinetics Studies of N^O-, O^N^O-, and N^N- Schiff Base Mn Complexes as Highly Active Catalysts in the Ring-Opening Polymerization of rac-Lactides","authors":"Mnqobi Zikode,&nbsp;Asanda Ngwenya,&nbsp;Tabea Becker,&nbsp;Sonja Herres-Pawlis,&nbsp;Stephen. O. Ojwach","doi":"10.1002/ejic.202500126","DOIUrl":"https://doi.org/10.1002/ejic.202500126","url":null,"abstract":"<p>A series of manganese complexes derived from (imino)phenol/pyridine proligands have been synthesized, structurally characterized and used as catalysts in the ring-opening polymerization (ROP) of <i>rac</i>-lactides (<i>rac</i>-LA). Reactions of MnCl₂·4H₂O salt with 2-[((2-hydroxyethyl)imino)methyl]phenol (<b>L1H</b>_<b>2</b>) afford a tetranuclear Mn(III) complex [Mn(<b>L1</b>)Cl]₄ (<b>Mn1</b>). Separately, treatment of MnCl₂·4H₂O with 2-[((2-methoxyethyl)imino)methyl]phenol (<b>L2H</b>) gave the mononuclear Mn(II) complex [Mn(<b>L2</b>)₂(CH₃OH)₂] (<b>Mn2</b>). Further, reactions of (imino)pyridine proligands ((E)-2-((pyridine-2-ylmethylene)amino)ethan-1-ol (<b>L3H</b>) and (E)-N-(2-methoxyethyl)-1-(pyrid-2-yl)methanimine (<b>L4</b>)) with MnCl₂·4H₂O afforded polynuclear Mn(II) complexes [Mn(<b>L3H</b>)Cl₂]₃ (<b>Mn3</b>) and [Mn(<b>L4</b>)Cl₂]₃ (<b>Mn4</b>), respectively. The molecular structure of <b>Mn1</b> established the tridentate binding mode of the dianionic alkoxy-(imino)phenol proligand ((<b>L1</b>^<b>2−</b>)) through the phenoxo and pendant-arm alkoxy-oxygen and the imine-nitrogen atoms. In contrast, the molecular structure of <b>Mn2</b> showed that the ether-(imino)phenol pro-ligand (<b>L2H</b>) is monoanionic (<b>L2</b>^<b>−</b>) and bidentately coordinated to the Mn(II) metal center through the phenoxo-oxygen and the imine-nitrogen atoms. The dinuclear complex <b>Mn3</b> contains a neutral N^N bidentately bound proligand (<b>L3H</b>). All the complexes (<b>Mn1</b>–<b>Mn4</b>) formed active catalysts in ROP of <i>rac</i>-LA with the propagation rate constant <i>k</i>_p of up to (4.25 ± 0.15) × 10⁻² L mol⁻¹ s⁻¹. The polymers obtained were atactic biased (<i>P</i>_r = 0.55–0.59), produced with moderate control over average-number molecular weights and were moderately dispersed (<i>Đ</i> up to 1.8) under melt conditions.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500126","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614995","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":"Selective Recognition Behavior of Arginine and Histidine Using an Anionic Luminescent Metal-Organic Material Stabilized by Cationic Amine: Steady State and Time-Resolved Luminescence Studies","authors":"Sayani Hui,&nbsp;Sahil Azam,&nbsp;Subhajit Dutta,&nbsp;Sudip Kumar Mondal,&nbsp;Partha Mahata","doi":"10.1002/ejic.202500042","DOIUrl":"https://doi.org/10.1002/ejic.202500042","url":null,"abstract":"<p>A new Eu-based metal-organic material, [Eu(CAM)₂(H₂O)] 0.5H₂Pip·H₂O, [CAM = chelidamate and H₂Pip = diprotonated piperazine], <b>1,</b> was synthesized by hydrothermal technique. Structure elucidation of compound <b>1</b> was done by single-crystal X-ray diffraction. The connectivity between Eu³⁺ ions and chelidamate ligands forms anionic dimeric metal-organic structures stabilized by interdimer O<span></span>H···O hydrogen bond interactions involving the free hydroxyl groups and carboxylate oxygen atoms. The O<span></span>H···O hydrogen bonds connect each dimeric unit with four other dimeric units to form a supramolecular 2D structure with rhombus grid topology. The 2D anionic hydrogen-bonded structures are further stabilized through N<span></span>H···O hydrogen bond interactions by involving piperazinediium ion to form an overall 3D supramolecular assembly. pH-dependent luminescence studies of compound <b>1</b> confirmed its stable nature in the pH range of 1–11. Luminescence turn-off behaviors of compound <b>1</b> were observed in the presence of two amino acids, for example, L-arginine (Arg) and L-histidine (His), in water. Luminescence decay processes and lifetime values confirmed that the quenching of luminescence of compound <b>1</b> by arginine is due to both static and dynamic quenching, but in the case of histidine, the quenching is purely static in nature.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614996","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":"Zeolitic Octahedral Metal Oxides for Catalysis","authors":"Zhuoyuan Chen,&nbsp;Zhenxin Zhang","doi":"10.1002/ejic.202500105","DOIUrl":"https://doi.org/10.1002/ejic.202500105","url":null,"abstract":"<p>Zeolitic octahedral metal oxides (ZOMOs) are crystalline microporous transition metal oxides, built from transition metal-oxygen clusters and inorganic linkers. The material shows both microporosity and redox property, which processes both advantages of zeolites and transition metal oxides. This concept outlines five ZOMO frameworks (ZOMO-1 to ZOMO-5) with tunable pore geometries and elemental diversity, enabling to tune the structure and chemical composition, which leads to tuning the catalytic activity of the materials. ZOMOs exhibit exceptional catalytic performance in selective oxidation, oxidative degradation, and H₂ evolution. Despite progress, there are still challenges in structure diversity and atomic-level structural control in the field of ZOMOs. Addressing these will advance ZOMOs as sustainable catalysts for energy and environmental applications.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615486","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: Complexes of d- and f-metal Ions with a Redox-Active and Highly Symmetric Truxenone Ligand: Effect of Cations and Coordination on Distortions of Radical Anions and Singlet-Triplet Transitions in Dianions (Eur. J. Inorg. Chem. 14/2025)","authors":"Kira D. Krivenko,&nbsp;Alexander F. Shestakov,&nbsp;Maxim A. Faraonov,&nbsp;Alexey V. Kuzmin,&nbsp;Salavat S. Khasanov,&nbsp;Akihiro Otsuka,&nbsp;Hideki Yamochi,&nbsp;Hiroshi Kitagawa,&nbsp;Dmitri V. Konarev","doi":"10.1002/ejic.202581401","DOIUrl":"https://doi.org/10.1002/ejic.202581401","url":null,"abstract":"<p><b>The Front Cover</b> shows truxenone (Tr), which has high C_3h symmetry and degenerated LUMO. It forms salts and complexes. Calculations predict Jahn–Teller distortions for Tr^⋅− that are enhanced by the asymmetric approach of Cp*₂Co⁺ to Tr^⋅−. The dianions should have a triplet state, but the asymmetric approach of Cs⁺ to the oxygen atoms of Tr²⁻ stabilizes the singlet ground state. Radical anions of Tr^⋅− coordinate with Tb^III(TMHD)₃ and Mn^II(acac)₂ providing asymmetric spin density localization on the coordinated oxygen atom and strong magnetic exchange of the ligand and paramagnetic metal spins. More information can be found in the Research Article by D. V. Konarev and co-workers (DOI: 10.1002/ejic.202400760).\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 14","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202581401","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144131513","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}