European Journal of Inorganic Chemistry最新文献

{"title":"Slab Rotation by Transition-Metal Relocation in the Layered Zintl Phase Li2ZnSi","authors":"Xian-Juan Feng,&nbsp;Alim Ormeci,&nbsp;Yurii Prots,&nbsp;Matej Bobnar,&nbsp;Ulrich Burkhardt,&nbsp;Marcus Schmidt,&nbsp;Mitja Krnel,&nbsp;Bodo Böhme,&nbsp;Frank. R. Wagner,&nbsp;Michael Baitinger,&nbsp;Ulrich Schwarz","doi":"10.1002/ejic.202500276","DOIUrl":"https://doi.org/10.1002/ejic.202500276","url":null,"abstract":"<p>The layered Zintl phase Li₂ZnSi is a structural analog of intercalated graphite with hexagonal layers of Zn and Si atoms separated by Li atoms (space group <i>P</i>6₃/<i>mmc</i>, <i>a</i> = 4.2458(2) Å, <i>c</i> = 8.224(1) Å). Single-crystal X-ray diffraction reveals Zn relocation into the center of the Zn₃Si₃ rings in 4% of the hexagonal layers. The Zn relocation is coupled with Li migration. The resulting 2D defects can be modeled either as 60° slab rotations or, alternatively, as layer translations by <i><b>k</b></i> = 1/3 [1,−1,0]. Li₂ZnSi shows metal-type electrical resistivity (ρ = 1.18 μΩ m at 300 K) and exhibits significantly enhanced diamagnetism, suggesting orbital contributions akin to those in graphite. This study demonstrates transition-metal mobility in a layered Zintl phase, generating localized 2D defects that leave the local coordination of each atom unchanged. This mechanism is relevant for understanding defect tolerance in structurally related electrode materials.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 27","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500276","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196547","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":"Hepta-Coordinated Mono- and Diorganotin(IV) Compounds with N3O2 Chelating Hydrazone Ligand","authors":"Tushar S. Basu Baul,&nbsp;Avishek Khatiwara,&nbsp;Andrew Duthie,&nbsp;Herbert Höpfl,&nbsp;David Mroß,&nbsp;Klaus Jurkschat","doi":"10.1002/ejic.202500343","DOIUrl":"10.1002/ejic.202500343","url":null,"abstract":"<p>A series of organotin(IV) complexes featuring the pro-ligand 2,6-diacetylpyridine bis(2-methylbenzoylhydrazone) (H₂L^Me) and various axial ligands have been synthesized. The reactions of H₂L^Me with R₂SnO (where R = Me, <i>n</i>-Bu, <i>n</i>-Oct, or <i>t</i>-Bu) and <i>n-</i>BuSnCl₃ in anhydrous toluene yielded the seven-coordinate complexes [Me₂Sn(L^Me)] (<b>1</b>), [<i>n</i>-Bu₂Sn(L^Me)] (<b>2</b>), [<i>n</i>-Oct₂Sn(L^Me)] (<b>3</b>), [<i>t</i>-Bu₂Sn(L^Me)] (<b>4</b>), and [<i>n</i>-BuSn(L^Me)Cl] (<b>5</b>), respectively. Subsequent treatment of complex <b>5</b> with NaN₃ and NH₄SCN afforded the corresponding isothiocyanate and azide derivatives, [<i>n</i>-BuSn(L^Me)N₃] (<b>6</b>), and [<i>n</i>-BuSn(L^Me)NCS] (<b>7</b>), respectively. Single crystal X-ray diffraction studies confirmed that the tin centers in complexes <b>1</b>, <b>2</b>, <b>4</b>, <b>6</b>, and <b>7</b> adopt a seven-coordinate geometry with a pentagonal bipyramidal configuration. The κ-<i>N</i>^<i>3</i><i>O</i>^<i>2</i> donor set of the ligand occupies the equatorial plane, while the axial positions are occupied by either two R groups, or one R group and one Cl, N₃, or NCS ligand, depending on the specific complex. In addition to X-ray diffraction analysis, all complexes <b>1</b>−<b>7</b> are characterized using Fourier transform infrared spectroscopy, high-resolution mass spectrometry , and solution-state Fourier transform nuclear magnetic resonance spectroscopy. The structural distortion within the SnN₃O₂ equatorial plane, attributed to positional shifts of the Sn(IV) center, are also discussed.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057928","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":"Variation of the Redox Properties and Coordination Chemistry of Redox-Active Aromatic Diguanidine Ligands with the Substitution Pattern","authors":"Maximilian Schulz,&nbsp;Andrei Poddelskii,&nbsp;Hannah A. Bohnert,&nbsp;Frederik Eckhardt,&nbsp;Lukas Hirner,&nbsp;Simone Leingang,&nbsp;Elisabeth Kaifer,&nbsp;Hans-Jörg Himmel","doi":"10.1002/ejic.202500346","DOIUrl":"https://doi.org/10.1002/ejic.202500346","url":null,"abstract":"<p>The redox properties of organic molecules like quinones are generally tuned by substitutions at the π-conjugated system or by changing the size of the π-conjugated core. Here, it analyzes the change of the redox properties within a series of isomeric molecules, differing only in the substitution pattern of the groups responsible for the redox activity. The seven redox-active molecules studied in this work, all composed of two guanidino and two thiolato substituents attached to a benzene core, can be reversibly oxidized to the dications, with the radical monocations as intermediate redox states, but the redox potentials and the potential separations between the first and second redox steps vary significantly with the substitution pattern. Distinct hyperfine coupling patterns observed in the EPR spectra of the radical monocations, in alliance with quantum-chemical calculations are used to show that, depending on the substitution pattern, semiquinonato-type or allyl radical–allyl cation-like structures are adopted. Reactions with Cu^II salts give different results depending on the substitution pattern, the copper coligands, and the guanidino group. Paramagnetic dinuclear Cu^II complexes with the neutral molecule as bridging ligand or diamagnetic Cu^I compounds with the redox-active molecules in their oxidized, dicationic redox state are formed.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 27","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500346","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196544","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":"[Au(CO)2][UF6]–Synthesis, Crystal Structure, Raman Spectroscopy, and Quantum-Chemical Calculations of the Nonclassical Carbonyl Compound","authors":"Tobias B. Wassermann,&nbsp;Antti J. Karttunen,&nbsp;Florian Kraus","doi":"10.1002/ejic.202500340","DOIUrl":"https://doi.org/10.1002/ejic.202500340","url":null,"abstract":"<p>The oxidation of Au powder with UF₆ in anhydrous hydrogen fluoride (aHF) under a CO atmosphere yields the previously reported nonclassical carbonyl [Au(CO)₂][UF₆], with Au<span></span>C bond lengths of 1.971(10) and 1.973(10) Å and C<span></span>O bond lengths of 1.146(15) and 1.088(13) Å. Its composition is now proven by the determination of its crystal structure and powder X-ray diffraction on the bulk phase. A Raman spectrum is successfully recorded and the CO vibration is observed at 2250 cm⁻¹. The nonclassical carbonyl compound [Au(CO)₂][UF₆] is synthesized by reacting Au powder, CO, and UF₆ in aHF. Its crystal structure is determined by single-crystal X-ray diffraction for the first time. Quantum-chemical calculations with the PBE0 hybrid density functional theory method (DFT-PBE0) for the crystal structure of [Au(CO)₂][UF₆] and the [Au(CO)₂]⁺ cation in the gas phase are carried out to allow for a comparison and assignment of the Raman bands.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 28","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500340","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145271910","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":"Lanthanide-Binding Lanmodulin-Based Peptides: Insights from Advanced Mass Spectrometry Techniques","authors":"Sophie M. Gutenthaler-Tietze,&nbsp;Lena J. Daumann,&nbsp;Patrick Weis","doi":"10.1002/ejic.202500258","DOIUrl":"https://doi.org/10.1002/ejic.202500258","url":null,"abstract":"<p>Selective peptide ligands for lanthanides (Ln) have multiple applications in, for example, Ln-separation and recycling or as lanthanide-binding tags. Optimizing peptides for Ln-binding can be cumbersome and many techniques need high sample volumes. Here short 12-aminoacid peptides are investigated based on the metal-binding loops of the natural Ln-binding protein lanmodulin with advanced gas-phase techniques such as ion mobility spectrometry, collision-induced dissociation, and electrospray ionization to gain insight into binding residues and possible differences between sequences. Both the natural sequences as well as peptides that are synthesized in “reverse” order are investigated and it is found that the trends observed in solution measurements are well reproduced by gas-phase measurements.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 26","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500258","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135809","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: Hydrogenation of CO2 to Methanol by a Nickel Pincer Catalyst and Mechanistic Investigations by Density Functional Theory Studies (Eur. J. Inorg. Chem. 21/2025)","authors":"Aman Mishra,&nbsp;Koushik Makhal,&nbsp;Dev Raj,&nbsp;Swarnasree Pasupalak,&nbsp;Bhabani S. Mallik,&nbsp;Ebbe Nordlander,&nbsp;Sumanta Kumar Padhi","doi":"10.1002/ejic.70000","DOIUrl":"10.1002/ejic.70000","url":null,"abstract":"<p><b>The Front Cover</b> demonstrates how a nickel pincer catalyst was used to hydrogenate CO₂ into methanol at moderate temperatures in both aqueous and solid–gas phases. Compared to the aqueous phase, the solid-gas phase demonstrated greater efficiency. By hydrogenating tagged CO₂ in the presence of base, GC-MS verified the production of methanol. More information can be found in the Research Article by B. S. Mallik, E. Nordlander, S. K. Padhi and co-workers (DOI: 10.1002/ejic.202500138).\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 21","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70000","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725504","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":"Cover Feature: Refinement of Crystal Structure and its Application for Catalytic Materials (Eur. J. Inorg. Chem. 21/2025)","authors":"Gabriel Ribeiro da Silva,&nbsp;Gabriel Alves da Silva,&nbsp;João Pedro Dias Querino,&nbsp;Luiz Gustavo Possato","doi":"10.1002/ejic.70001","DOIUrl":"10.1002/ejic.70001","url":null,"abstract":"<p><b>The Cover Feature</b> presents a vibrant cyclic flowchart illustrating the catalytic research workflow. It begins with X-ray diffraction (XRD) data, followed by Rietveld refinement and extraction of structural parameters. These insights guide catalyst design/modification, which is then tested in catalytic reactions, culminating in catalytic activity results, thus completing the research cycle. More information can be found in the Review by L. G. Possato and co-workers (DOI: 10.1002/ejic.202500051).\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 21","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725632","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 Simple Micellar Gold Catalyst Supported by a Hydrophilic Phosphinoferrocene Amidosulfonate Ligand","authors":"David Rezazgui,&nbsp;Jiří Schulz,&nbsp;Frank Uhlig,&nbsp;Petr Štěpnička","doi":"10.1002/ejic.202500338","DOIUrl":"10.1002/ejic.202500338","url":null,"abstract":"<p>The design of micellar catalysts is instrumental in transferring metal-catalyzed organic reactions into aqueous reaction media and enabling catalyst reuse. Herein, it is reported that phosphinoferrocene amidosulfonate Ph₂PfcC(O)NHCH₂SO₃(HNEt₃) (<b>1</b>, fc = ferrocene-1,1′-diyl) and its chlorogold(I) complex [AuCl(<b>1</b>-κ<i>P</i>)] (<b>8</b>) form stable micelles in water. The latter compound is found to be an efficient, self-activating catalyst for the gold-catalyzed cyclization of <i>N</i>-propargyl benzamide into 4,5-dihydro-5-methylene-2-phenyloxazole in a water-ethyl acetate mixture. Structure determination of <b>8</b>·½CH₂Cl₂ reveals extensive hydrogen bonding between the polar amidosulfonate pendants, in line with the compound's surfactant-like behavior. Density functional theory calculations of the plausible LAu⁺ type catalyst suggest a possible in situ self-activation of complex <b>8</b> in water via chloride loss, possibly facilitated by the amidosulfonate group and the formation of Au(I)-aqua species.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500338","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145058046","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":"Synthesis and Optical Properties of Ln2Ln′2-Tetranuclear Lanthanide(III) Complexes","authors":"Maria Storm Thomsen,&nbsp;Andrew D. Bond,&nbsp;Dominic S. Wright","doi":"10.1002/ejic.202500348","DOIUrl":"https://doi.org/10.1002/ejic.202500348","url":null,"abstract":"<p>A set of structurally related heterotetranuclear lanthanide(III) (Ln) complexes containing Ln¹₂Ln²₂ cores has been synthesized as potential downshifting materials for solar applications. The Ln¹₂Ln²₂ complexes can be regarded as intermediate model systems between classical doped systems and dinuclear molecular systems. The choice of Ln¹ and Ln² is based on commonly used codoped solid-state systems to evaluate the effect of energy transfer in the tetranuclear unit. The complexes are obtained by a new systematic approach involving the reactions of stable, solvent-free dinuclear homometallic precursors (Ln¹₂ + Ln²₂<span>→</span>Ln¹₂ + Ln²₂)<span>.</span> The new complexes Tb₂Yb₂q₆(hfac)₄(μ₃-OH)₂ (<b>Tb</b>_<b>2</b><b>Yb</b>_<b>2</b>) and Nd₂Tb₂q₆(hfac)₄(μ₃-OH)₂ (<b>Nd</b>_<b>2</b><b>Tb</b>_<b>2</b>) (q⁻ = 8-hydroxyquinolate; hfac⁻ = hexafluoroacetylacetonate), show emission both in the visible and near-IR regions. In both <b>Nd</b>_<b>2</b><b>Tb</b>_<b>2</b> and <b>Tb</b>_<b>2</b><b>Yb</b>_<b>2</b>, a reduction in the excited-state lifetime of the donor, Tb³⁺ is observed relative to the acceptor-free complex, Tb₂Y₂q₆(hfac)₄(μ₃-OH)₂ (<b>Tb</b>_<b>2</b><b>Y</b>_<b>2</b>), thus, signifying an energy transfer to the acceptors, Nd³⁺ or Yb³⁺, respectively. Overall, this work provides a versatile approach to controlling the aggregation and composition of mixed-lanthanide complexes while introducing new building blocks for exploring Ln-to-Ln′ energy transfer in discrete heteropolynuclear systems.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 30","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500348","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145341806","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: (Eur. J. Inorg. Chem. 20/2025)","authors":"","doi":"10.1002/ejic.202582001","DOIUrl":"10.1002/ejic.202582001","url":null,"abstract":"<p>\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 20","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202582001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647374","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}