European Journal of Inorganic Chemistry最新文献_第8页

Front Cover: (Eur. J. Inorg. Chem. 19/2025) 封面：（欧元）j . Inorg。化学19/2025)

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-14 DOI: 10.1002/ejic.202581901

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A Family of Luminescent Halido Cadmates with Bifunctional Diammonium Cations 一类具有双官能团二铵离子的发光卤代化合物

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-14 DOI: 10.1002/ejic.202500264

Meng Yang, Ralph Otmar Kusche, Sebastian Anhäuser, Jakob Möbs, Gregor Witte, Johanna Heine

{"title":"A Family of Luminescent Halido Cadmates with Bifunctional Diammonium Cations","authors":"Meng Yang, Ralph Otmar Kusche, Sebastian Anhäuser, Jakob Möbs, Gregor Witte, Johanna Heine","doi":"10.1002/ejic.202500264","DOIUrl":"10.1002/ejic.202500264","url":null,"abstract":"This study presents the synthesis, single crystal structures, and optical properties of a series of six halido cadmates featuring the diammonium cations 4-(ammoniomethyl)pyridinium (H2AMP2+) and 4-(ammonioethyl)pyridinium (H2AEP2+). The chlorido cadmates (H2AMP)2Cd3Cl10·4H2O (1) and (H2AEP)4Cd5Cl18 (2) feature complex polymeric anion motifs, while the bromido and iodio cadmates (H2AMP)CdBr4·H2O (3), (H2AEP)CdBr4 (4), (H2AMP)CdI4 (5), and (H2AEP)CdI4 · H2O (6) are composed of mononuclear {CdX4} units (X = halogen) packed in different arrangements. (H2AEP)4Cd5Cl18 (2) displays a phase transition between 100 K and room temperature, which is studied in detail. All compounds show decomposition temperatures above 180 °C. Optical bandgaps of the compounds are estimated in the range from 3.4 to 4.4 eV, with all compounds showing significant sub-bandgap absorption. Compounds 1–6 also show broad low-temperature emission centred between 1.95 and 2.5 eV.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500264","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905303","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}

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RuIII(edta) Complex-Mediated Oxidation of Hydrazine to Nitrogen: Spectral, Electrochemical, and Kinetic Studies RuIII（edta）配合物介导的肼氧化制氮：光谱、电化学和动力学研究

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-12 DOI: 10.1002/ejic.202500269

Olga Impert, Alessandro Niorettini, Titas Kumar Mukhopadhyay, Debabrata Chatterjee

{"title":"RuIII(edta) Complex-Mediated Oxidation of Hydrazine to Nitrogen: Spectral, Electrochemical, and Kinetic Studies","authors":"Olga Impert, Alessandro Niorettini, Titas Kumar Mukhopadhyay, Debabrata Chatterjee","doi":"10.1002/ejic.202500269","DOIUrl":"10.1002/ejic.202500269","url":null,"abstract":"The [RuIII(edta)pz]− complex (edta4− = ethylenediaminetetraacetate; pz = pyrazine), despite being a substantially weak electron-accepting oxidant (E1/2 = 0.24 V vs Normal Hydrogen Electrode for RuIII/II couple), can effect the oxidation of hydrazinium ion (NH2NH3+) to nitrogen (N2) selectively with concomitant formation of the [RuII(edta)pz]2− product complex. The time course of the reaction is followed spectrophotometrically at the characteristic band of [RuII(edta)(pz)]2− (λmax = 462 nm) as a function of [NH2NH3+]T, pH, and temperature. A mechanism involving hydrogen atom transfer from NH2NH3+ to the remote N-atom of the coordinated pyrazine in the [RuIII(edta)pz]− complex is proposed for the aforesaid oxidation reaction. Electrochemical and spectroelectrochemical studies reveal that RuIII(edta)pz]− can act as a “redox relay” for the electrochemical oxidation of NH2NH3+ to N2 at 0.5 V (vs saturated calomel reference electrode) under argon atmosphere. Density functional theory (DFT) calculations are utilized to optimize the structures of the reactant and product complexes. Detailed mechanistic proposals in agreement with the spectral, electrochemical, kinetic, and DFT computation data are presented for the aforesaid oxidation reaction.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144914872","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}

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Electronic and Photophysical Properties of a Heterometallic Ru(II)–Cu(I) Kuratowski Complex: Insights from Spectroscopy and Density Functional Theory Calculations 异质金属Ru(II) -Cu (I) Kuratowski配合物的电子和光物理性质：来自光谱学和密度泛函理论计算的见解

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-09 DOI: 10.1002/ejic.202500190

Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Dirk Volkmer

{"title":"Electronic and Photophysical Properties of a Heterometallic Ru(II)–Cu(I) Kuratowski Complex: Insights from Spectroscopy and Density Functional Theory Calculations","authors":"Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Dirk Volkmer","doi":"10.1002/ejic.202500190","DOIUrl":"10.1002/ejic.202500190","url":null,"abstract":"Polynuclear metal complexes offer tunable electronic properties that are valuable for photocatalysis and molecular electronics. Herein, the synthesis and characterization of a poly-heteronuclear Kuratowski complex, [RuIICuI4(Me2bta)6(PPh3)4] is presented. This complex is designed to investigate the electronic coupling between strongly reducing Cu(I) centers and a Ru(II) ion, mediated by a highly symmetric framework of triazolate ligands. Electrochemical studies reveal coupled redox behavior between Ru(II) and Cu(I), while UV–vis spectroscopy shows an overlapping Ru- and Cu-centered metal-to-ligand charge transfer (MLCT) band, redshifted in comparison to its {RuIIZnII4} analog. Despite this, fluorescence lifetime measurements indicate that ultrafast nonradiative relaxation limits electron transfer between the metal centers. Density functional theory (DFT) and time-dependent-DFT calculations confirm that ligand-field effects, rather than direct Ru–Cu interactions, drive the MLCT redshift. These observations offer tentative insights into excited-state dynamics and highlight design aspects for controlling electronic communication in polynuclear systems.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500190","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881474","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}

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Phosphazene Base Mediated (sp3)CH Functionalization with CO2 and CS2 磷腈碱介导的（sp3）C - H与CO2和CS2的功能化

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-09 DOI: 10.1002/ejic.202500298

Katharina Wels, Beate Neumann, Jan-Hendrik Lamm, Hans-Georg Stammler, Berthold Hoge

{"title":"Phosphazene Base Mediated (sp3)CH Functionalization with CO2 and CS2","authors":"Katharina Wels, Beate Neumann, Jan-Hendrik Lamm, Hans-Georg Stammler, Berthold Hoge","doi":"10.1002/ejic.202500298","DOIUrl":"10.1002/ejic.202500298","url":null,"abstract":"The activation of weakly acidic (sp3)CH bonds in substrates such as fluoroform (HCF3), perfluoroethane (HC2F5), and acetonitrile (H3CCN) remains a fundamental challenge in synthetic chemistry. We report that the phosphazene base {(Et2N)3P=N}3P=NtBu (EtP4) enables the selective deprotonation of these molecules when combined with electrophilic small molecules such as CO2 or CS2. This cooperative approach affords a variety of structurally diverse anions, including CF3-substituted dithiocarboxylates and novel five- and six-membered cyano-thiolato-dithioheterocycles resulting from activation of H3CCN. The ring compounds are stable in air and are characterized by single-crystal X-ray diffraction, infrared spectroscopy, and mass spectrometry. These findings expand the scope of metal-free base/electrophile systems for (sp3)CH functionalization and provide synthetic access to isolable carbanions derived from otherwise inert substrates.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500298","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915090","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}

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A Vanadophosphate Hybrid [(VIVO)3(PO4)2(dien)3]: Integrating Phosphate into Vanadate Systems Leads to Enhanced Thermal Stability and Modulated Magnetism 钒磷酸盐杂化物[(VIVO)3(PO4)2(dien)3]：将磷酸盐整合到钒酸盐体系中可以增强热稳定性和调制磁性

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1002/ejic.202500230

Xiu-Zhen Xie, Ran Chen, Jin-Xiao Mi, Shao-Yi Zeng, Jia-Hui Liao, Jia-Yu Song, Wu-Hua Chen

{"title":"A Vanadophosphate Hybrid [(VIVO)3(PO4)2(dien)3]: Integrating Phosphate into Vanadate Systems Leads to Enhanced Thermal Stability and Modulated Magnetism","authors":"Xiu-Zhen Xie, Ran Chen, Jin-Xiao Mi, Shao-Yi Zeng, Jia-Hui Liao, Jia-Yu Song, Wu-Hua Chen","doi":"10.1002/ejic.202500230","DOIUrl":"https://doi.org/10.1002/ejic.202500230","url":null,"abstract":"The physicochemical behavior of a substance is fundamentally governed by its crystal structure and can be precisely tuned through isostructural chemical substitution. This atomic replacement typically occurs among atoms or ions within the same group or block of the periodic table, characterized by similar ionic radii, oxidation states, and electronegativity profiles. However, when such substitutions involve elements across different periodic blocks with distinct electronic configurations, they enable nontraditional routes for tuning material properties, often deviating from conventional structure–property relationships. In the present investigation, a novel organic vanadyl phosphate complex, [(VIVO)3(PO4)2(dien)3] (1) (dien = diethyltriamine, C4H13N3), is successfully synthesized through a hydrothermal reaction involving dien, NH4VO3, and Na3PO4 in aqueous medium, achieved by substituting a p-block element (phosphorus) for a d-block element (vanadium) in the prototype structure. Single-crystal X-ray diffraction analysis reveals that compound 1 maintains isostructural characteristics with its mixed-valence vanadium analog, [V5O11(dien)3], wherein the [VVO4] moiety is replaced by the [PO4] tetrahedron. The incorporation of phosphorus and vanadium in compound 1, along with their respective oxidation states, is verified through comprehensive spectroscopic and analytical techniques. The results reveal that compound 1 exhibits substantial differences in physical properties, particularly in magnetic response and thermal stability, compared to its structural analog.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 28","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145272183","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}

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Automated Assembly Modeling of Metal–Organic Polyhedra 金属有机多面体的自动化装配建模

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1002/ejic.202500115

Aleksandar Kondinski, Andrea M. Oyarzún-Aravena, Simon D. Rihm, Jiaru Bai, Sebastian Mosbach, Jethro Akroyd, Markus Kraft

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Hydrothermal Synthesis and Characterization of the Melamine-Based Second-Harmonic Generation Material HgCl2(C3N6H6) 三聚氰胺基二次谐波材料HgCl2（C3N6H6）的水热合成及表征

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1002/ejic.202500256

Melena Groß, Patrick Schmidt, Carl P. Romao, David Enseling, Thomas Jüstel, Mykhailo Brytskyi, Scott Kroeker, Hans-Jürgen Meyer

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Three Single-Ion Magnet Candidates from Erbium(III) Squarate Complexes in Relation with a Square-Antiprismatic Coordination Structure 铒（III）方配合物中与方-反棱镜配位结构相关的三个候选单离子磁铁

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-30 DOI: 10.1002/ejic.202500184

Rina Takano, Yasutaka Kitagawa, Takayuki Ishida

{"title":"Three Single-Ion Magnet Candidates from Erbium(III) Squarate Complexes in Relation with a Square-Antiprismatic Coordination Structure","authors":"Rina Takano, Yasutaka Kitagawa, Takayuki Ishida","doi":"10.1002/ejic.202500184","DOIUrl":"10.1002/ejic.202500184","url":null,"abstract":"Mononuclear [Er(sq)(Hsq)(H2O)6]•(H2O) (sq = squarate, C4O42−) and heteroleptically bridged 3D polymer [Er2(sq)2(ox)(H2O)4]n (ox = oxalate, C2O42−) were newly prepared. The Arrhenius plot for the alternating-current magnetic susceptibility data clarified the effective energy barriers for magnetization reversal, Ueff/kB = 42.0(7) K at a direct-current bias field of 1000 Oe for the former and 21.7(8) K at 800 Oe for the latter. They are greater than that of known 2D [Er2(sq)3(H2O)8]n. All of the erbium(III) coordination structures investigated here can be described approximately as a square antiprism with a slight variation in axial compression within a D4d symmetry framework. To elucidate a suitable degree of D4d compression, the complete-active-space self-consistent-field calculation was carried out on the discrete neutral molecule [Er(sq)(Hsq)(H2O)6] and its modifications after anisotropically upto 10% elongation or compression along the principal axis. The calculated energy gap between the ground and the first excited states in the Stark sublevels is 151.5 cm−1 for the original [Er(sq)(Hsq)(H2O)6] molecule, and the gap became wider with more compressed as well as elongated ErO8 structures. The gap is highly sensitive to the compressed/elongated modification, justifying the variety and diversity of the single-ion magnet characteristics observed.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905525","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}

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α,β-Alkylation Reactions Catalyzed by Ruthenium Triphenylphosphine Complexes Bearing Substituted Pyridine–Quinoline Based Ligands 含取代吡啶喹啉配体的三苯基膦钌配合物催化的α，β-烷基化反应

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-29 DOI: 10.1002/ejic.202500154

Nikolaos Zacharopoulos, Panagiotis-Georgios Kanellopoulos, Evangelos Bakeas, Antigoni Cheilari, Gregor Schnakenburg, Athanassios Chrissanthopoulos, Athanassios Philippopoulos

{"title":"α,β-Alkylation Reactions Catalyzed by Ruthenium Triphenylphosphine Complexes Bearing Substituted Pyridine–Quinoline Based Ligands","authors":"Nikolaos Zacharopoulos, Panagiotis-Georgios Kanellopoulos, Evangelos Bakeas, Antigoni Cheilari, Gregor Schnakenburg, Athanassios Chrissanthopoulos, Athanassios Philippopoulos","doi":"10.1002/ejic.202500154","DOIUrl":"10.1002/ejic.202500154","url":null,"abstract":"Herein, a series of ruthenium(II) bis-triphenylphosphine complexes comprising substituted pyridine–quinoline based ligands for the efficient α-alkylation of ketones with primary alcohols, via the borrowing hydrogen methodology, are reported. β-alkylation of secondary alcohols by primary alcohols is also reported. The reactions are catalyzed by the ruthenium complexes [RuCl2(8-Mepq)(PPh3)] (1), [RuCl2(6′-Mepq)(PPh3)2] (2), [RuCl2(4,6′-Me2pq)(PPh3)2)] (3), including [RuCl2(4-Mepq)(PPh3)2] (4), and [RuCl2(pq)(PPh3)2] (5). Mass spectrometry, elemental analysis, and 31P NMR data reveal that 1 is a five-coordinate 16-electron ruthenium(II) complex with one triphenylphosphine ligand, as opposed to 2–5, which hold two and are six-coordinate. Theoretical calculations suggest that 1 is stabilized by a nonclassical RuCl(1)···H(2) interaction between a hydrogen atom of the appended methyl group and an adjacent chlorine atom. By NMR spectroscopy, different isomers of 2 and 3 have been detected. For the α-alkylation of benzyl alcohol with acetophenone, all complexes selectively provided 1,3-diphenylpropan-1-one as the sole product, within an hour. The β-alkylation of 1-phenylethanol with benzyl alcohol under the same conditions is less selective. As salient features of this report we could mention that these catalytic systems operate with easily accessible and in high yields air-stable catalysts, within a shorter period compared to known ruthenium complexes.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881148","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}

引用次数: 0