European Journal of Inorganic Chemistry最新文献

{"title":"Instigating Visible Light Inspired DNA Impairment by ROS Harvesting Ir(III)-Cyclometallated Imidazophenanthroline Complexes Against MDA-MB-231 Cells","authors":"Sreejani Ghosh,&nbsp;Priyankar Paira","doi":"10.1002/ejic.202400769","DOIUrl":"https://doi.org/10.1002/ejic.202400769","url":null,"abstract":"<p>Difficulties to abate the vehemence of deleterious triple-negative breast cancer (TNBC) is an ardent issue in the current context of anticancer research due to the lack of a selective treatment modality. To address this issue, herein we have endeavored to establish the imidazophenanthroline-based Ir(III)-cyclometallated heteroleptic complexes, suited for the one-photon photodynamic therapy (OP-PDT) under irradiation of visible light (400–700 nm) possessing long-lived excited triplet state and significant photostability. Among three synthesized complexes, [<b>L1Ir</b>], [<b>L2Ir</b>], [<b>L3Ir</b>], the complex [<b>L2Ir</b>] has been recognized as the most competent complex to exhibit selective phototoxicity (IC₅₀=3.8 <i>μ</i>M; PI^c=78.94) in MDA-MB-231 triple-negative breast cancer cells. The significant phototoxicity of the complexes has arisen due to the production of reactive singlet oxygen (¹O₂) following the type-II pathway (Φ_s=0.26). Also, the complexes have shown the proficiency in oxidation of reduced nicotinamide adenine dinucleotide (NADH) (TOF=37.82 h⁻¹) indicating the possibility of reactive oxygen species (O₂⋅⁻, ⋅OH) generation through type-I pathway upon visible light irradiation. Along with this, intracellular glutathione (GSH) depletion capabilities have endued the complexes to unarm the TNBC cells in front of the profuse amount of ROS instigating the programmed cell death (PCD) through substantial DNA damage.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741408","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":"Photocatalytic Nitrogen Fixation Materials and Mechanistic Features: State of the Art and Future Perspectives","authors":"Costanza Tedesco,&nbsp;Giulia Giovilli,&nbsp;Lorenzo Malavasi","doi":"10.1002/ejic.202400686","DOIUrl":"https://doi.org/10.1002/ejic.202400686","url":null,"abstract":"<p>photocatalysis, nitrogen photofixation, material chemistry, heterojunctionThe essential role ammonia occupies, considering both its major industrial use for nitrogen-rich fertilizers and the possibility of being utilized as medium for energy storage, clashes with the environmental drawbacks of the Haber-Bosch process, its main production method. This review investigates the potential of photocatalytic nitrogen fixation (PNF) as an eco-friendly approach, driven by solar energy and inspired by natural nitrogenase enzymes. It traces the historical development of nitrogen fixation methods and focuses on recent advancements in photocatalytic materials, including metal oxides, sulfides, and composite systems. Strategies to enhance catalytic performance – including doping, defect engineering, and heterojunction construction – are showcased, thus providing a way to mitigate low conversion efficiency and electron-hole recombination. The work concludes by presenting emergent materials that could revolutionize the field, offering new paths for sustainable ammonia production.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400686","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645683","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. 5/2025)","authors":"","doi":"10.1002/ejic.202580501","DOIUrl":"https://doi.org/10.1002/ejic.202580501","url":null,"abstract":"<p>\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 5","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202580501","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431218","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":"CuII and ZnII Complexes with 1,3,4-Thiadiazole-5-Thiomethyl-Based Diamide","authors":"Ana Júlia Zimmermann Londero,&nbsp;Ulrich Abram,&nbsp;Maximilian Roca Jungfer,&nbsp;Prof. Vânia Denise Schwade","doi":"10.1002/ejic.202400736","DOIUrl":"https://doi.org/10.1002/ejic.202400736","url":null,"abstract":"<p>The diamide ligand, <i>N</i>,<i>N’</i>-bis(5-thiomethyl-1,3,4-thiadiazol-2-yl)-2,6-pyridinedicarboxamide (<b>H₂L</b>) in its solvate form has two planar acetylamino groups, which are twisted slightly from the plane of the 5-thiomethyl-thiadiazole rings. The ligand reacts with: (i) copper(II) salts forming binuclear and pentanuclear compounds; (ii) zinc(II) acetate leading to an anionic trinuclear complex. The molecular structures of [Cu₂(μ-H₂O)(L)₂] (<b>1</b>), [Cu₅(dmf)(μ₃-OH)₂(L)₃(L^b)]_0.8[Cu₅(μ₃-OH)₂(L)₃(L^b)]_0.2 ⋅ 0.5DMF⋅H₂O (<b>2</b>) and [Zn(H₂O)₂(dmf)₄][Zn₃(μ₃-OH)(L)₃]₂ ⋅ 2DMF ⋅ H₂O (<b>3</b>) (where {L^b}²⁻ represents the partially hydrolyzed ligand) were confirmed by X-ray diffractometry. We have found that compound <b>1</b> can exist as two tautomers: the aqua bridge in [Cu₂(μ-H₂O)(L)₂] and the hydroxy bridge in [Cu₂(μ-OH)(HL)(L)]. All compounds were characterized by elemental analysis and ESI mass spectrometry as well as FT-IR, Raman and UV-Vis spectroscopy. The luminescence properties of H₂L⋅DMF and compound <b>3</b> were investigated. Compound <b>3</b> has strong fluorescence with the emission band centered at 508 nm, and fluorescence lifetime of 1.44 ns. The potential of chalcogen bonding interactions in aroylamidothiadiazoles and their compounds is discussed based on DFT calculations. The <i>cis</i>-ketone-configuration of oxygen and sulfur is energetically favored over other potential rota- and tautomers. Most importantly, the deprotonation of the ligand increases the O ⋅ ⋅ ⋅ S interaction strength due to a larger negative charge at oxygen leading to increased conformational stability in the coordination compounds. A massively increased delocalization of the nitrogen atoms lone pair in the deprotonated state compared to the protonated state, however, may be the main reason for the observed conformation.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645751","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":"A New Eosin Y and Hydroxybenzaldehyde Coupled Probe for Instantaneous Sensing of Cu2+ by Colorimetric and ‘Turn-off’ Fluorescence Methods","authors":"Arnab Chakraborty,&nbsp;Neeladri Das","doi":"10.1002/ejic.202400717","DOIUrl":"https://doi.org/10.1002/ejic.202400717","url":null,"abstract":"<p>Xanthene-based organic chemosensors for detecting metal ions are a topic of research. While Rhodamine and Fluorescein-based sensors are more common, fewer research articles exist on Eosin-based sensors. Herein, a new chemosensor (<b>EY-S</b>) is reported that was obtained efficiently in two high-yielding reaction steps from commercially procured Eosin Y. <b>EY-S</b> is a fluorescent molecule that can selectively detect cupric (Cu²⁺) ions in the presence of other competing metal ions. The colorimetric sensing of Cu²⁺ ions was studied using uv-vis spectroscopy. The green fluorescence of <b>EY-S</b> was effectively quenched by Cu²⁺ and quantified by fluorescence titration. A high magnitude of the Stern-Volmer (<i>K</i>_sv) constant advocated efficient quenching. Job's plot confirmed a 1 : 1 complexation ratio between <b>EY</b>−<b>S</b> and Cu²⁺. The association constant (<i>K</i>_a) for the host-guest complexation was determined to be 1.59×10⁵ M⁻¹. The limit of detection (LOD) associated with the detection of Cu²⁺ was 3.29 nM, indicating the high sensitivity of the <b>EY</b>−<b>S</b> sensor. Cu²⁺ detection was also tested using actual water samples collected from various sources, and EY−S′ performance remained uncompromised. The sensor could detect Cu²⁺ in acidic, neutral, and essential media, with the sensing being most efficient at higher pH. The <b>EY-S</b> sensor/probe could be easily recycled multiple times without significantly declining Cu²⁺ detection performance. A mechanism of binding between <b>EY-S</b> and Cu²⁺ was also proposed.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645957","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":"Functionalization of a Rhodamine-B Based Chemosensor onto Surfaces of Fe3O4, SBA-15 and H2Ti3O7 Support Substrates for Selective Fe3+ Ion Detection","authors":"Debajani Mallick,&nbsp;Sriparna Chatterjee,&nbsp;Mamata Mohapatra,&nbsp;Bamaprasad Bag","doi":"10.1002/ejic.202400728","DOIUrl":"https://doi.org/10.1002/ejic.202400728","url":null,"abstract":"<p>The major challenges in the chemosensing approach are the development of analytically uncomplicated and cost-effective method for the selective and sensitive detection of metal ions in the aqueous medium. Rhodamine derivatives have proven as efficient and effective chemosensory probes for selective and sensitive detection of different metal ions in the solution phase, predominantly in aqueous-organic medium, where the interaction of the probe and metal ion translated on signalling module expressed through dual mode photophysical output. A rhodamine-B-based probe <b>2</b>, incorporated with 3-nitrobenzaldehyde coupled (2-aminoethyl)-piperazinyl receptor, was developed to exhibit selective and sensitive detection of Fe³⁺ ions in aqueous-ethanol medium. Its spiro-cyclic ring-opening on Fe³⁺-complexation resulted in absorption and fluorescence spectral enhancements with concomitant colour change, inferring to the structure-function module of signalling expressions and the extent of their magnitude has contributed the selectivity, sensitivity, interaction affinity, response time, reversibility and other parameters of efficient detection. The probe also exhibited similar photophysical output responses in the selective presence of Fe³⁺ ion on immobilization onto surfaces of silica-coated magnetite, SBA-15 and hydrogen titanate appended through amino-propyl-silyl linker. Apart from retaining the selectivity towards Fe³⁺ ions, these surface-functionalized inorganic support materials (<b>3</b>, <b>4</b>, and <b>5</b>) executed the signalling action in aqueous medium, enhancing their scope as efficient chemosensors for practical application. The effect of probe immobilization on the metal ion-induced photophysical signalling behaviour in these hybrid materials was evaluated with their X-ray diffraction pattern, FTIR spectral analysis, thermogravimetric analysis, FESEM images and elemental analysis, surface area determination and particle size analysis for establishing a structure-function correlation in their selective Fe³⁺ ion detection in aqueous suspension.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 11","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822192","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":"N,N,N′,N′-Tetrakis((1H-Pyrazol-3-Yl)methyl)-1,2-Ethanediamine Ligands as Versatile Scaffolds for Second Coordination Sphere Design","authors":"Corentin Pochet,&nbsp;Tristan Laurent,&nbsp;Dr. Mengmeng Wang,&nbsp;Prof. Aurelian Rotaru,&nbsp;Dr. Koen Robeyns,&nbsp;Prof. Yann Garcia,&nbsp;Prof. Michael L. Singleton","doi":"10.1002/ejic.202400835","DOIUrl":"https://doi.org/10.1002/ejic.202400835","url":null,"abstract":"<p>The polypyrazole-containing ligands, N,N,N′,N′-tetrakis((5-<i>tert-</i>Butyl-1<i>H</i>-pyrazol-3-yl)methyl)-1,2-ethanediamine (L1) and N,N,N′,N′-tetrakis((5-Phenyl-1<i>H</i>-pyrazol-3-yl)methyl)-1,2-ethanediamine (L2) were synthesized and shown to form hexadentate monometallic coordination compounds with Co^II, Ni^II, Cu^II and Zn^II metal ions. Exchange studies with the metal ions show binding preference in the order of Ni^II&gt;Co^II/Cu^II&gt;Zn^II. The compounds were confirmed by NMR, UV-Vis studies and the X-ray crystals structures of [Co(L1)](PF₆)₂, [Ni(L1)](PF₆)₂, [Cu(L1)]ClPF₆, [Zn(L1)](PF₆)₂, and [Ni(L2)]Cl_2. In the solid state, the arrangement of the bulky pyrazole units leads to the formation of two distinct cationic pockets containing the N−H groups of the pyrazoles. These cationic pockets are found to bind Cl⁻ or PF₆⁻ counterions through hydrogen bonding and anions titrations revealed good affinity for Cl⁻ and Br⁻. The compounds can be dehydronated up to two times using mild organic bases, highlighting the potential of these ligands to tune the electronic properties of the metal center.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 11","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822154","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":"Alkaline Earth Metal Nitride Chalcogenides, Ca6N2Se3, Sr6N2Se3 and Sr6N2Te3","authors":"Guowei Sun,&nbsp;Prof. Dr. Rainer Niewa","doi":"10.1002/ejic.202400763","DOIUrl":"https://doi.org/10.1002/ejic.202400763","url":null,"abstract":"<p>The novel isotypic hexagonal alkaline earth metal nitride chalcogenides Ca₆N₂Se₃, Sr₆N₂Se₃ and Sr₆N₂Te₃ (<i>R</i><span></span><math></math>\u0000 (No.167); <i>Z</i>=6) were synthesized from Ca(Sr)/Na flux at 1173 K. The compounds belong to the rare class of ternary metal nitride chalcogenides. The structures feature the shortest Ca/Sr−N bonds within the regular trigonal antiprismatic coordination (Ca−N: 235.17(8); Sr−N: 251.20(6) pm). Two crystallographic distinct nitrogen atoms are coordinated in a trigonal antiprism and a twisted trigonal prism, respectively, and are alternatively condensed via trigonal trans-faces to form one-dimensional chains <span></span><math></math>\u0000. The chalcogenide ions in comparison realize rather ambiguous environments. Raman spectroscopic data are reported.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 9","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400763","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698929","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":"Does Fluorine Make a Difference? How Fluoro Groups Influence the (Structural) Properties of MOFs","authors":"Prof. Dr. Uwe Ruschewitz","doi":"10.1002/ejic.202400809","DOIUrl":"https://doi.org/10.1002/ejic.202400809","url":null,"abstract":"<p>Herein, the influence of fluorine substituents on the structural and physical properties of MOFs with aromatic carboxylate ligands is investigated. To achieve this, the focus is limited to a few widely used ligand classes, e. g. terephthalates or trimesates. It is shown that the torsion angle between the phenyl ring and the carboxylate groups plays a decisive role. This can also be transferred to more complex ligands. These considerations clearly show why there are isostructural variants of some MOFs with perfluorinated ligands known (e. g. MIL-53), while for others no successful synthesis has been reported up to now (e. g. HKUST-1). In order to investigate the influence of the fluorination of the linker on the properties of the corresponding MOFs, isostructural systems were analysed more specifically. It was found that the thermal and chemical stability decreases with fluorination, while the absorption of CO₂ in particular is enhanced. With regard to the specific surface area (<i>S</i>_BET), the results are contradictory.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 10","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400809","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740997","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 Stable Hexacoordinated Arsenic(V) Dication","authors":"Tomoki Yasui,&nbsp;Akane Chishiro,&nbsp;Masato Sakabe,&nbsp;Soichi Sato,&nbsp;Takashi Yumura,&nbsp;Kenji Kanaori,&nbsp;Kensuke Naka,&nbsp;Hiroaki Imoto","doi":"10.1002/ejic.202400819","DOIUrl":"https://doi.org/10.1002/ejic.202400819","url":null,"abstract":"<p>Polycations of main-group elements have emerged as a significant research focus in recent years. Hypercoordinated dications having heavier pnictogens, such as antimony (Sb) and bismuth (Bi), as a central atom have been extensively studied due to their large atomic radii. However, limited research has been conducted on the corresponding dications of lighter pnictogens such as phosphorus (P) and arsenic (As). In this study, we synthesized a 2-(2-pyridyl)phenyl (ppy)-ligated arsenic dication ([(ppy)₃As][SbCl₆]₂ and [(ppy)₃As]Cl₂) as a first example of novel hexacoordinated arsenic-centered dication species. This arsenic-centered dication species demonstrates remarkable stability at high temperatures and in hot water. Both experimental and computational analyses indicated that their exceptional stability is primarily due to strong As–N interactions. Notably, the arsenic-centered dication species exhibits greater stability than their antimony counterparts.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 12","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861522","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}