Chemistry - A European Journal最新文献_第2页

A Multistep Oxidative Cascade Reaction from a Naphthalenediol-Based pre-Ligand to a Tetranuclear Perylenequinone-Based FeIII Complex. 从基于萘二醇的前配体到基于过醌的四核 FeIII 复合物的多步氧化级联反应。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403690

Jasmin Finke, Jan Oldengott, Anja Stammler, Thorsten Glaser

{"title":"A Multistep Oxidative Cascade Reaction from a Naphthalenediol-Based pre-Ligand to a Tetranuclear Perylenequinone-Based FeIII Complex.","authors":"Jasmin Finke, Jan Oldengott, Anja Stammler, Thorsten Glaser","doi":"10.1002/chem.202403690","DOIUrl":"10.1002/chem.202403690","url":null,"abstract":"We have developed a family of dinuclear complexes using 2,7-disubstituted 1,8-naphthalenediol ligands that bind by molecular recognition to two neighboring phosphate diesters of the DNA backbone with the dinuclear CuII and NiII complexes exhibiting a severe cytotoxicity for human cancer cells. To increase the binding affinity, we intended to synthesize the corresponding dinuclear FeIII complex. Surprisingly, we obtained a tetranuclear FeIII perylene-based complex instead of the expected dinuclear FeIII naphthalene-based complex. In order to establish a rational and reproducible synthesis, we carefully analyzed this reaction. This revealed a multistep oxidative cascade reaction including the pre-coordination of FeII ions in the N3-binding pockets, the Lewis-acid assisted MOM-deprotection of the pre-ligand by the pre-oriented FeII ions, two oxidative aromatic C-C coupling reactions, oxidation of the perylene-based backbone and of FeII to FeIII. The careful analysis of bond lengths, HOMA indices (harmonic oscillation model of aromaticity), FTIR and UV-Vis-NIR spectra supported by DFT calculations reveals the presence of an aromatic 18-electron oxidized perylenequinone ligand backbone. In summary, a multistep cascade reaction involving in total a 10-electron oxidation has been established for the straight-forward synthesis of an unprecedented perylenequinone-based ligand system.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403690"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal Pyrazolyl-diphosphonate Pillared Materials as Heterogeneous Catalysts in the Mukaiyama-type Aerobic Olefin Epoxidation. 作为 Mukaiyama 型有氧烯烃环氧化作用中的异相催化剂的吡唑基二膦酸金属柱状材料。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403756

Nikolaos Giakoumakis, Elpiniki Chachlaki, Duane Choquesillo-Lazarte, Kostas D Demadis

引用次数: 0

The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth ComplexesThe Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes. 高价吡啶-二吡咯烷铋络合物的发射和电化学性质高价吡啶-二吡咯烷铋络合物的发射和电化学性质。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403761

Katharina L Deuter, Felix Kather, Michael Linseis, Michael Bodensteiner, Rainer Friedrich Winter

{"title":"The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth ComplexesThe Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes.","authors":"Katharina L Deuter, Felix Kather, Michael Linseis, Michael Bodensteiner, Rainer Friedrich Winter","doi":"10.1002/chem.202403761","DOIUrl":"10.1002/chem.202403761","url":null,"abstract":"We present a series of six hypervalent bismuth complexes Bi(R1PDPR2)X bearing ligands characterized by the pyridine-2,6-bis(pyrrolide) (PDP) structural motif. While bismuth holds considerable potential for facilitating efficient intersystem crossing (ISC), reports on phosphorescent molecular bismuth complexes are still scarce and mostly based on systems that exhibit inter‑ or intraligand charge transfer character of their optical excitations. Herein, the UV/vis absorptive, luminescent, and electrochemical properties of complexes Bi(R1PDPR2)X are explored, where the substituents R1 and R2, as well as the halide ligand X are varied. These compounds are characterized by an intense HOMO®LUMO transition of mixed ligand-to-metal charge transfer (LMCT) and interligand charge transfer (LL'CT) character, as shown by time-dependent density functional theory (TD-DFT) calculations. At 77 K in a 2-MeTHF matrix, these compounds exhibit red, long-lived phosphorescence with lifetimes ranging from 671 to 20 µs. Cyclic voltammetry measurements and TD-DFT calculations show that the substituents influence HOMO and LUMO energies to almost equal extent, resulting in nearly constant emission wavelengths throughout this series. Single-crystal X-ray diffraction studies of four of the six complexes exemplify the inherent Lewis acidity of the coordinated Bi3+ ion, in spite of its hypervalency.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403761"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Novel Methacryloyl-Masked NIR Fluorescent Probe for Detection of Cysteine and Its Application in Bioimaging. 用于检测半胱氨酸的新型甲基丙烯酰掩蔽近红外荧光探针及其在生物成像中的应用

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202402840

Prasad M Sonawane, Neha Jain, JunHyuk Kim, Su Jeong Park, Sandip V Mulay, Satish Balasaheb Nimse, David G Churchill

引用次数: 0

A Cascade Synthesis of Furo-Pyrrolo-Pyridines via Pd(II)-Catalyzed Dual N-H/C Annulative-Cyclization. 通过 Pd(II)-Catalyzed Dual N-H/C Annulative-Cyclization 级联合成呋喃并吡咯并吡啶。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403470

Hirendra Nath Dhara, Supriya Manna, Bhisma K Patel

引用次数: 0

Remarkable effect of stereoisomerism on the Am(III)/Ln(III) solvent extraction. New ligands for highly efficient separation of americium. 立体异构对 Am(III)/Ln(III) 溶剂萃取的显著影响。高效分离镅的新配体。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403056

Valentine S Petrov, Pavel S Lemport, Mariia V Evsiunina, Petr I Matveev, Paulina Kalle, Yulia V Nelyubina, Svetlana A Aksenova, Alexei D Averin, Alexei A Yakushev, Vitaly A Roznyatovsky, Roman V Zonov, Vladimir G Petrov, Igor P Gloriozov, Yuri A Ustynyuk, Valentine G Nenajdenko

{"title":"Remarkable effect of stereoisomerism on the Am(III)/Ln(III) solvent extraction. New ligands for highly efficient separation of americium.","authors":"Valentine S Petrov, Pavel S Lemport, Mariia V Evsiunina, Petr I Matveev, Paulina Kalle, Yulia V Nelyubina, Svetlana A Aksenova, Alexei D Averin, Alexei A Yakushev, Vitaly A Roznyatovsky, Roman V Zonov, Vladimir G Petrov, Igor P Gloriozov, Yuri A Ustynyuk, Valentine G Nenajdenko","doi":"10.1002/chem.202403056","DOIUrl":"https://doi.org/10.1002/chem.202403056","url":null,"abstract":"Two novel 1,10-phenanthroline-2,9-diamide ligands were constructed based on 2-phenylpyrrolidine and obtained as pure diastereomers. These ligands demonstrated advanced properties in liquid-liquid extraction tests. They revealed high efficiency of americium(III) extraction alongside with the record values of selectivity in the separation of americium from light lanthanides from strongly acidic media. An abrupt increase of extraction efficiency when moving along the lanthanide series from lanthanum to lutetium was observed. The examination of the extraction behavior of pure diastereomeric forms revealed noticeable differences in their selectivity while maintaining the overall extraction trend. The explanation of the discovered patterns was elucidated by a comprehensive study of the ability of the ligands to bind lanthanide nitrates in solutions. All the data collected (UV-vis and NMR titration, X-ray analysis of resulting complexes, solvation numbers estimation) were supported by quantum chemical calculation. These data clearly indicated that in case of light lanthanides the formation of 1:1 complexes is most preferable. In the same time, complexes with heavy lanthanides, such as ytterbium and lutetium, exist as ionic pairs which may consist of [L2M]z+ cations counterbalanced by metallates anions, which may result in formation of unusual composition species L2M2 or even L4M5 clusters.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403056"},"PeriodicalIF":3.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stereodivergent Macrocyclization in Dynamic Chiral Confinement. 动态手性封闭中的立体发散大环化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202404207

Linfeng Tan, Tianyi Zheng, Yongsheng Li, Myongsoo Lee

引用次数: 0

Orthogonal Functionalization of Oxo-Graphene Nanoribbons. 氧化石墨烯纳米带的正交功能化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403645

Lucia Merkel, Christof Neumann, Christian E Halbig, Anton Habel, Xin Chen, Andrey Turchanin, Siegfried Eigler

引用次数: 0

Scalable Bulk Synthesis of Phase-Pure γ-Sn3N4 as a Model for an Argon-Flow-Mediated Metathesis Reaction. 以氩气流介导的 Metathesis 反应为模型，大规模合成相纯 γ-Sn3N4

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403745

Mirjam Zipkat, Aylin Koldemir, Theresa Block, Claude Ceniza, Teak D Boyko, Sebastian Kläger, Reinhard M Pritzl, Alexander Moewes, Rainer Pöttgen, Stefan S Rudel, Wolfgang Schnick

{"title":"Scalable Bulk Synthesis of Phase-Pure γ-Sn3N4 as a Model for an Argon-Flow-Mediated Metathesis Reaction.","authors":"Mirjam Zipkat, Aylin Koldemir, Theresa Block, Claude Ceniza, Teak D Boyko, Sebastian Kläger, Reinhard M Pritzl, Alexander Moewes, Rainer Pöttgen, Stefan S Rudel, Wolfgang Schnick","doi":"10.1002/chem.202403745","DOIUrl":"https://doi.org/10.1002/chem.202403745","url":null,"abstract":"Nitrides represent a promising class of materials for a variety of applications. However, bulk synthesis remains a challenging task due to the stability of the N2 molecule. In this study, we introduce a simple and scalable approach for synthesizing nitride bulk materials. Moderate reaction temperatures are achieved by using reactive starting materials, slow and continuous mixing of the starting materials, and by dissipating heat generated during the reaction. The impact on the synthesis of using different starting materials as nitrogen source and the influence of a flux were examined. γ-Sn3N4 was selected as the model compound. The synthesis of pure γ-Sn3N4 bulk material on a large scale has still been a challenge, although a few synthesis methods were already described in the literature. Here we synthesized γ-Sn3N4 by metathesis reaction of argon-diluted SnCl4 with Li3N, Mg3N2 or Ca3N2 as nitrogen sources. Products were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, dynamic flash combustion analysis, hot gas extraction analysis, X-ray photoelectron spectroscopy, Mössbauer spectroscopy and X-ray absorption and emission spectroscopy. Additionally, single-crystal diffraction data of γ-Sn3N4, previously unavailable, were successfully collected.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403745"},"PeriodicalIF":3.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nutation spectroscopy of a weakly interacting heterobimetallic spin system. 弱相互作用异重金属自旋系统的变异光谱。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403521

Jordan Appleton, Nolwenn Le Breton, Sylvie Choua, Romain Ruppert, Athanassios Boudalis

{"title":"Nutation spectroscopy of a weakly interacting heterobimetallic spin system.","authors":"Jordan Appleton, Nolwenn Le Breton, Sylvie Choua, Romain Ruppert, Athanassios Boudalis","doi":"10.1002/chem.202403521","DOIUrl":"10.1002/chem.202403521","url":null,"abstract":"The use of VIV and CuII spins to design weakly coupled and dissymmetric spin systems has been examined. Such systems were synthesized using porphyrin-based complexes, with external coordination sites allowing for the formation of dimers via a PdII linker ion. Continuous-wave (CW) Electron Paramagnetic Resonance (EPR) spectroscopy allowed the unequivocal magnetic characterization of the mononuclear precursors V and Cu. The porphyrin dimer VPdCu presented a broad and overlapped spectrum that was more pronounced than for the previously reported VPdV, hinting at the effect of weak interspin interactions between dissimilar spins. Pulsed EPR experiments on V, VPdV and VPdCu samples diluted in a diamagnetic matrix confirmed that this complication is also present in the Field-Swept Echo-Detected (FSED) spectra of the heterometallic VPdCu system. Despite the strongly overlapped field-swept spectra, spin nutation experiments revealed two distinct oscillations in the case of VPdCu, which are assigned to transitions with different spin characters. Remarkably, coherence is retained above liquid nitrogen temperatures for all complexes, in particular up to 295 K for V and VPdV and 150 K for VPdCu.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403521"},"PeriodicalIF":3.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0