European Journal of Inorganic Chemistry最新文献_第7页

Mechanism of Phenol Oxidation by CuCl2 CuCl2氧化苯酚的机理

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-18 DOI: 10.1002/ejic.202500113

Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu

{"title":"Mechanism of Phenol Oxidation by CuCl2","authors":"Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu","doi":"10.1002/ejic.202500113","DOIUrl":"10.1002/ejic.202500113","url":null,"abstract":"Although copper-catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase-type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl2 salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl2 in the presence of weakly coordinating tripodal N-nitrosated ligand L3NO have been illustrated, while a closely related tripodal copper(II) complex L3HCuCl2 (2) of the corresponding non-nitrosated ligand L3H does not react with the phenolic substrates. Phenol reactions with CuCl2 in the presence of the L3NO ligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with ΔH‡ = 15.13 kcal mol−1, ΔS‡ = −9.6 eu, and kinetic isotope effect k2(ArOH)/k2(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl2 are capable of facilitating a proton-coupled electron transfer (PCET) pathway.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915146","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}

引用次数: 0

Dinuclear Benzene Linker Bis(pyrazolyl)amine Cobalt(II) Complexes and their Application as Selective Ethylene Dimerization Catalysts 双（吡唑基）胺钴（II）配合物及其作为选择性乙烯二聚化催化剂的应用

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-18 DOI: 10.1002/ejic.202500204

Francis K. Migwi, George S. Nyamato, Stephen O. Ojwach

{"title":"Dinuclear Benzene Linker Bis(pyrazolyl)amine Cobalt(II) Complexes and their Application as Selective Ethylene Dimerization Catalysts","authors":"Francis K. Migwi, George S. Nyamato, Stephen O. Ojwach","doi":"10.1002/ejic.202500204","DOIUrl":"10.1002/ejic.202500204","url":null,"abstract":"Reactions of synthons N,N′-(1,4-phenylenebis(methylene))bis(2-(1 H-pyrazol-1-yl)ethan-1-amine) (L1), N,N′-(1,4-phenylenebis(methylene))bis(2-(3,5-dimethyl-1 H-pyrazol-1-yl)ethan-1-amine) (L2), N,N′-(1,4-phenylenebis(methylene))bis(2-(3,5-di-tert-butyl-1 H-pyrazol-1-yl)ethan-1-amine) (L3), and N,N′-(1,3-phenylenebis(methylene))bis(2-(3,5-dimethyl-1 H-pyrazol-1-yl)ethan-1-amine) (L4) with CoCl2 produce the dinuclear cobalt(II) complexes [Co2(L1)Cl4] (Co1), [Co2(L2)Cl4] (Co2), [Co2(L3)Cl4] (Co3), and [Co2(L4)Cl4] (Co4), respectively. These new complexes are characterized using fourier transform-infra red and ultra-violet (UV)–Visible spectroscopies, elemental analysis, and single crystal X-ray crystallography diffraction for complexes Co2 and Co3. The molecular structures of Co2 and Co3 confirm the formation of the dinuclear cobalt species. Activation of the precatalysts Co1–Co4 with either EtAlCl2 or Me3Al, affords active (up to 5.26 × 105 g·mol−1Co h−1) and selective ethylene dimerization (>98%) catalysts. The steric parameters of the coordinated ligands, as dictated by the substituents on the pyrazolyl ring, largely controll both the activity and regioselectivity of the resultant catalysts.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500204","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881192","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

Tin Porphyrins with Germyl- and Silylalkynyl Substitution: Synthesis, Characterization, and Solar Cell Applications 具有Germyl-和silyl炔基取代的锡卟啉：合成、表征和太阳能电池应用

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-18 DOI: 10.1002/ejic.202500188

Doris M. Grössl, Bettina Schlemmer, Virginia Lafranconi, Nina M. Tasch, Christoph Garstenauer, Lara Rezo, Melanie Moosbrugger, Michaela Flock, Roland C. Fischer, Thomas Rath, Ana Torvisco, Gregor Trimmel, Frank Uhlig

{"title":"Tin Porphyrins with Germyl- and Silylalkynyl Substitution: Synthesis, Characterization, and Solar Cell Applications","authors":"Doris M. Grössl, Bettina Schlemmer, Virginia Lafranconi, Nina M. Tasch, Christoph Garstenauer, Lara Rezo, Melanie Moosbrugger, Michaela Flock, Roland C. Fischer, Thomas Rath, Ana Torvisco, Gregor Trimmel, Frank Uhlig","doi":"10.1002/ejic.202500188","DOIUrl":"10.1002/ejic.202500188","url":null,"abstract":"Porphyrins, known for their extensive biological functions, have been adapted for diverse applications through modification of their substitution patterns and metal centers. This study focuses on synthesizing tin porphyrins with germyl- and silyl-alkenyl substituents, addressing gaps in structural characterization and solubility behavior. Additionally, their potential in bulk-heterojunction solar cells is investigated. The synthetic pathways for these porphyrins are established, and their structural properties are analyzed using single crystal X-ray diffraction. The solubility of the synthesized porphyrin (5) is compared with meso-tetraaryl and meso-tetraalkyl free-base porphyrins. Electrochemical properties are studied through cyclic voltammetry, and density functional theory (DFT) calculations provide insights into the highest occupied and lowest unoccupied molecular orbitals. Despite promising optical and electrochemical properties, the solar cell performance of the synthesized porphyrins remains moderate, highlighting the need for further functionalization to enhance the power conversion efficiency.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500188","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915147","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

Synthesis of Metastable Wurtzite Cu–in-Doped ZnS Photocatalysts via Molten Salt Treatment 熔盐法合成亚稳纤锌矿铜掺杂ZnS光催化剂

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-18 DOI: 10.1002/ejic.202500252

Tomohiro Kawase, Yoshio Kobayashi, Haruki Nagakawa

{"title":"Synthesis of Metastable Wurtzite Cu–in-Doped ZnS Photocatalysts via Molten Salt Treatment","authors":"Tomohiro Kawase, Yoshio Kobayashi, Haruki Nagakawa","doi":"10.1002/ejic.202500252","DOIUrl":"10.1002/ejic.202500252","url":null,"abstract":"Herein, the crystallization process of doped ZnS photocatalysts using a molten salt treatment in air is explored. When ZnS-based photocatalysts with low crystallinity and a zincblende structure are heated in molten salt under conditions of a short holding time at high temperatures, the structure transitions from zincblende to the metastable wurtzite phase at 600 °C, which is significantly lower than the bulk transition temperature (1020 °C). Furthermore, with a longer holding time, ZnS reverted to the stable zincblende phase. This phenomenon is attributed to the unique crystal growth behavior of the nanoparticles in the molten salt environment. The evaluation of the synthesized photocatalysts reveals that ZnS with a wurtzite structure exhibits particularly high photocatalytic activity. Additionally, Cu and In co-doping induce visible-light responsiveness, achieving hydrogen evolution with a higher external quantum efficiency (EQE) than that of molten-salt-treated CdS photocatalysts synthesized in previous studies. The selective formation of nanoparticles with a metastable wurtzite structure or microparticles with a stable zincblende structure could be controlled by varying the holding time at 600 °C. Thus, Cu–In-doped ZnS photocatalysts may potentially be used as Cd-free alternative photocatalysts and semiconductor electrode materials.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500252","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905463","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

Front Cover: Synthesis and Characterization of A3[ReO4][ReO3N] and A′2[ReO3N] (A = Rb, Cs; A′ = K, Cs) (Eur. J. Inorg. Chem. 17/2025) 封面：A3[ReO4][ReO3N]和A ' 2[ReO3N]的合成与表征(A = Rb, Cs；A ' = K, c)(欧元；j . Inorg。化学17/2025)

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-18 DOI: 10.1002/ejic.202581701

Désirée Badea, Christoph Lenting, Michael Hanrath, Jörn Bruns

引用次数: 0

Design, Synthesis, and Modulation of Valence Tautomeric Binuclear Cobalt Compounds with Redox-Active Bridged Ligands 具有氧化还原活性桥接配体的价互变异构双核钴化合物的设计、合成和调制

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-17 DOI: 10.1002/ejic.202500103

Lei Zhang, Zhi-Kun Liu, Ling-Tai Yue, Jie-Sheng Hu, Yu-Meng Zhao, Jun Tao

{"title":"Design, Synthesis, and Modulation of Valence Tautomeric Binuclear Cobalt Compounds with Redox-Active Bridged Ligands","authors":"Lei Zhang, Zhi-Kun Liu, Ling-Tai Yue, Jie-Sheng Hu, Yu-Meng Zhao, Jun Tao","doi":"10.1002/ejic.202500103","DOIUrl":"10.1002/ejic.202500103","url":null,"abstract":"Valence tautomeric (VT) compounds are a kind of bistable materials characterized by intramolecular electron transfer (ET). This study focuses on the controlled synthesis and performance modulation of compounds exhibiting VT behavior. Through the design of redox-active ligands and the adoption of auxiliary ligands and counter-anions, three compounds are successfully prepared, that is, [{Co(tpa)}2(Lcat−cat)](PF6)2·8H2O·4CH3OH (1), [{Co(tpa)}2(Lcat−cat)](BPh4)2·2CH2Cl2 (2), and [{Co(dpaOMe)}2(Lcat−cat)](BPh4)2·6CH3CN (3), respectively, where Lcat−cat = 6,6′-((1 E,1′E)-hydrazine-1,2-diylidenebis(methaneylylidene)) bis(3,5-di-tert-butylbenzene-1,2-diol), tpa = tris(2-pyridinylmethyl) amine, and dpaOMe = 2-methoxy-N,N-bis(pyridine-2-ylmethyl)aniline. Structural, magnetic, and spectroscopic analyzes reveal that 1 and 2 remain in the {CoIII-cat-cat-CoIII} configuration, whereas 3 undergoes VT transition near 350 K. Comparative studies highlight that the modification of auxiliary ligand from tpa to dpaOMe significantly enhances the intramolecular ET capability. This finding provides valuable insights into how ligand engineering regulates VT behavior, offering a foundation for the design of advanced functional materials.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 20","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647525","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}

引用次数: 0

Biogenic Synthesis for Silver and Copper Nanoparticles Supported by Lemon Peel Derived Microfibers of Cellulose and their High Performance Catalytic and Antibacterial Applications 柠檬皮纤维素微纤维负载纳米银和纳米铜的生物合成及其高效催化和抗菌应用

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-17 DOI: 10.1002/ejic.202500145

Meng Chen, Zhixin He, Yingrui Song, Fen Wu, Fangyu Fu, Xia Li, Yanlan Wang

{"title":"Biogenic Synthesis for Silver and Copper Nanoparticles Supported by Lemon Peel Derived Microfibers of Cellulose and their High Performance Catalytic and Antibacterial Applications","authors":"Meng Chen, Zhixin He, Yingrui Song, Fen Wu, Fangyu Fu, Xia Li, Yanlan Wang","doi":"10.1002/ejic.202500145","DOIUrl":"10.1002/ejic.202500145","url":null,"abstract":"This article reports the first biogenic synthesis of silver and copper nanoparticles supported by thread-like lemon-peel-derived microfibers of cellulose (LMFC) with a width ranged from 13.4 to 17.8 μm. Biomass-derived LMFC is prepared via smashing lemon peel using a food blender and employed as simultaneous reducing and stabilizing agents for the preparation of heterogeneous Ag@LMFC, Cu@LMFC, and AgCu@LMFC. Fourier-transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) manifests that the polyol groups in LMFC acted as the reducing agent. The nanoparticles anchored on Ag@LMFC and AgCu@LMFC disperse well and the sizes are 14.1 ± 3.0 and 14.4 ± 3.2 nm, respectively, which are much smaller than the ones (27.8 ± 5.3 nm) in Cu@LMFC due to their different reducing potentials. The obtained AgCu@LMFC (0.5 mmol%, TOF = 9761 h−1) is the most efficient reusable silver/copper nanoparticle reported for 4-nitrophenol reduction so far, with catalytic efficiency even reaching that of precious metals. Moreover, Ag@LMFC exhibits much higher antibacterial activity than Cu@LMFC against both Gram-negative and Gram-positive bacteria. This biogenic synthesis brings a sustainable alternative to conventional chemical methods for fabrication heterogeneous silver and copper nanoparticles with high performance catalytic and antibacterial applications.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 21","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725443","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}

引用次数: 0

Photothermal Coupling Effect Enhances CO2 Conversion to Solar Fuels over Ni/CeZrO2 Catalyst Ni/CeZrO2催化剂促进CO2转化为太阳能燃料的光热耦合效应

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1002/ejic.202500130

Boyi Yang, Yuan-Hao Zhu, Ruoxuan Peng, Yuan Yin, Changjun You, Junhai Wang, Yitao Si, Jiancheng Zhou

{"title":"Photothermal Coupling Effect Enhances CO2 Conversion to Solar Fuels over Ni/CeZrO2 Catalyst","authors":"Boyi Yang, Yuan-Hao Zhu, Ruoxuan Peng, Yuan Yin, Changjun You, Junhai Wang, Yitao Si, Jiancheng Zhou","doi":"10.1002/ejic.202500130","DOIUrl":"10.1002/ejic.202500130","url":null,"abstract":"Zirconium dioxide (ZrO2) has been applied to convert CO2 into valuable chemicals, thereby contributing to energy harvesting in a sustainable manner. However, the large bandgap of ZrO2 has bottlenecked its photocatalytic water splitting efficiency, hindering its application in advancing more economic CO2 and H2O conversion. Here, a cerium–zirconium solid solution (CeZrO2) with Ni loading is synthesized and its strengths in catalyzing photothermal redox reaction with CO2 and H2O is demonstrated. The experimental findings demonstrate that the CO yield of the Ni/CeZrO2 catalyst is remarkably augmented to 673.5 μmol g−1 h−1 under concentrated light radiation (4.0 W cm−2), which is a substantial increase of 70.6-fold in CO yield and 69.73-fold in energy conversion efficiency when compared to the 9.4 μmol g−1 h−1 yield observed under standard irradiation conditions (0.4 W cm−2). This success to the decrease in bandgap with the incorporation of Ce and the synergized catalytic mechanism is attributed. Specifically, these sites achieve rational accommodation of reactants and accelerate the reaction kinetic. This work sheds light on the modification strategy for broad bandgap catalysis for efficient photothermal energy conversion.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 19","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615535","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}

引用次数: 0

Organic Linker Effect on Iodine Adsorption in Thorium-Based UiO-66-Type Metal Organic Frameworks 有机连接剂对钍基uio -66型金属有机骨架吸附碘的影响

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-13 DOI: 10.1002/ejic.202500162

Abhishek Sharma, Bal Govind Vats, Swayam Kesari, Rajendra Kumar Sharma, Jitendra Bahadur, Suresh Chandra Parida

{"title":"Organic Linker Effect on Iodine Adsorption in Thorium-Based UiO-66-Type Metal Organic Frameworks","authors":"Abhishek Sharma, Bal Govind Vats, Swayam Kesari, Rajendra Kumar Sharma, Jitendra Bahadur, Suresh Chandra Parida","doi":"10.1002/ejic.202500162","DOIUrl":"10.1002/ejic.202500162","url":null,"abstract":"Thorium-based UiO-66/67 metal-organic frameworks (MOFs) are studied among the most promising radioactive iodine traps to achieve sustainable clean nuclear energy. Here, seven MOFs, namely, Th-BDC, Th-1,4-NDC, Th-ADC, Th-ABDC, Th-2,6-NDC, Th-BiPhDC, and Th-BiPyDC (where BDC= benzene-1,4-dicarboxylic acid; 1,4-NDC = naphthalene-1,4-dicarboxylic acid; ADC = anthracene-9,10-dicarboxylic acid; ABDC = 2-aminobenzene-1,4-dicarboxylic acid; BiPhDC = 1,1′-biphenyl-4,4′-dicarboxylic acid; BiPyDC = 2,2′-bipyridyl-5,5′-dicarboxylic acid), are synthesized and characterized employing powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, surface area measurement, Fourier-transform infrared, and Raman spectroscopy. MOFs having large linker lengths, namely, Th-2,6-NDC, Th-BiPhDC, and Th-BiPyDC, are collapsed during solvent drying. I2 vapor adsorption studies are carried out, and the I2@MOFs are characterized. MOFs with similar linker lengths but different numbers of aromatic rings (Th-BDC, Th-1,4-NDC, Th-ADC) have similar SSA (specific surface area) normalized I2 adsorption capacities (≈0.9 g/g). Among the UiO-66-type MOFs, ThBDC stands out to have highest I2 adsorption capacity of ≈1.7 g/g due to the presence of an electron-donating group on the aromatic ring. This study provides the rationale to design better MOFs for I2 adsorption and gives insight that the electron density modulated by the electron-donating group on the linker is more significant than increasing the number of aromatic rings in UiO-66 family.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 21","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725364","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}

引用次数: 0

Synthesis, Characterization, Magnetic Properties, and DFT Investigations of Heterobimetallic Nickel–Lanthanide LNiIILnIII (Ln = Ce, Gd, Tb, Dy) Complexes Supported by Schiff Base Ligands 席夫碱配体负载的镍镧系杂双金属LNiIILnIII （Ln = Ce, Gd, Tb, Dy）配合物的合成、表征、磁性能及DFT研究

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-06-13 DOI: 10.1002/ejic.202500229

Fatma Darkebira, Fatéma Zohra Chiboub Fellah, Lotfi Belkhiri, Thierry Roisnel, Souhir El Hassasna, Thierry Guizouarn, Abdou Boucekkine, Fabrice Pointillart

{"title":"Synthesis, Characterization, Magnetic Properties, and DFT Investigations of Heterobimetallic Nickel–Lanthanide LNiIILnIII (Ln = Ce, Gd, Tb, Dy) Complexes Supported by Schiff Base Ligands","authors":"Fatma Darkebira, Fatéma Zohra Chiboub Fellah, Lotfi Belkhiri, Thierry Roisnel, Souhir El Hassasna, Thierry Guizouarn, Abdou Boucekkine, Fabrice Pointillart","doi":"10.1002/ejic.202500229","DOIUrl":"10.1002/ejic.202500229","url":null,"abstract":"Four Schiff base complexes LNiLn (Ln = Ce (2), Gd (3), Tb (4), and Dy (5), H2L= N,N′-bis(3-methoxysalicylaldiimine)-1,3-propylene-2-ol)) are synthesized from the precursor LNi (1) moieties. However, compound 2, which crystallizes in the tetragonal system, differs from the other isostructural three 3, 4, and 5 congeners. The dc magnetic studies reveal ferromagnetic interaction between the Ni(II) (S = 1) and the trivalent lanthanide (Ln(III) = Gd, Tb, and Dy) but not for Ce(III) in agreement with the computational results. The dynamic magnetic investigations highlight field-induced single-molecule magnet behaviors at 2 K for Ln(III) = Ce, Tb, and Dy. In case of compound 4, it is determined that the slow magnetic relaxation occurs through an Orbach process only with Δ = 19.1(3) K and τ0 = 3.99(4) × 10−7 s (H = 1200 Oe). Electronic structures and magnetic properties have been investigated theoretically using relativistic density functional theory calculations combined with the broken symmetry approach for the magnetic properties. The results indicate a Ferro character for 3 (+1.03 cm−1), 4 (+5.44 cm−1), and 5 (+1.35 cm−1), and an antiferromagnetic (AF) behavior for complex 2 (−2.82 cm−1), in agreement with experimental magnetic susceptibility measurements. Moreover, the computed Mayer and Nalewajski–Mrozek Ni(II)–Ob and Ob–Ln(III) bond orders are found to be higher for 2 than for 3, 4, and 5, correlating well with the AF and Ferro character of each species.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500229","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905299","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