Inorganica Chimica Acta最新文献

英文中文

Advancing luminescent Sensing: Harnessing Metal-Organic frameworks for enhanced detection and analysis

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-27 DOI: 10.1016/j.ica.2024.122520

Amrit Krishna Mitra , Nitisha Chakraborty

Metal-organic frameworks (MOFs) are porous, crystalline materials composed of metal ions or clusters coordinated with organic linkers. Their structural and functional properties, such as large surface area, tunable pore size, and adjustable luminescence, can be tailored through careful selection of metal centers, organic ligands, and reaction conditions. These attributes make MOFs highly effective in applications including gas storage, catalysis, energy storage, and sensing.

This review emphasizes luminescent metal–organic frameworks (LMOFs), which exhibit photoluminescence arising from their metal centers, organic linkers, or encapsulated guest molecules. Their tunable luminescence enables sensitive and selective detection of diverse analytes, making them promising tools for environmental pollutant sensing. LMOFs have demonstrated exceptional performance in detecting pollutants such as pesticides, antibiotics, explosives, volatile organic compounds (VOCs), toxic gases, small molecules, radioactive ions, and heavy metals, with advantages including high sensitivity, selectivity, and recyclability.

To introduce the fundamentals of MOFs, this article outlines their nature, classification, and nomenclature. It also provides an overview of synthetic methods, along with modifications aimed at optimizing their properties. The review highlights recent advancements in MOF-based luminescent sensors and their applications in environmental monitoring.

By summarizing the progress and challenges in MOF research, this mini-review aims to inspire further development of luminescent MOFs and their practical applications in addressing environmental contamination.

{"title":"Advancing luminescent Sensing: Harnessing Metal-Organic frameworks for enhanced detection and analysis","authors":"Amrit Krishna Mitra , Nitisha Chakraborty","doi":"10.1016/j.ica.2024.122520","DOIUrl":"10.1016/j.ica.2024.122520","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are porous, crystalline materials composed of metal ions or clusters coordinated with organic linkers. Their structural and functional properties, such as large surface area, tunable pore size, and adjustable luminescence, can be tailored through careful selection of metal centers, organic ligands, and reaction conditions. These attributes make MOFs highly effective in applications including gas storage, catalysis, energy storage, and sensing.</div><div>This review emphasizes luminescent metal–organic frameworks (LMOFs), which exhibit photoluminescence arising from their metal centers, organic linkers, or encapsulated guest molecules. Their tunable luminescence enables sensitive and selective detection of diverse analytes, making them promising tools for environmental pollutant sensing. LMOFs have demonstrated exceptional performance in detecting pollutants such as pesticides, antibiotics, explosives, volatile organic compounds (VOCs), toxic gases, small molecules, radioactive ions, and heavy metals, with advantages including high sensitivity, selectivity, and recyclability.</div><div>To introduce the fundamentals of MOFs, this article outlines their nature, classification, and nomenclature. It also provides an overview of synthetic methods, along with modifications aimed at optimizing their properties. The review highlights recent advancements in MOF-based luminescent sensors and their applications in environmental monitoring.</div><div>By summarizing the progress and challenges in MOF research, this mini-review aims to inspire further development of luminescent MOFs and their practical applications in addressing environmental contamination.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"578 ","pages":"Article 122520"},"PeriodicalIF":2.7,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143347475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Luminescent tetranuclear Ag(I)/Cu(I) cubane clusters: Investigating argentophilicity, cuprophilicity, and mixed argento-cuprophilicity

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-26 DOI: 10.1016/j.ica.2024.122517

Rais Ahmad Khan , Mohammad H. Jaafar , Arman D. Hadi , Huda Alsaeedi , Ali Alsalme

In this article, we have investigated the luminescence properties and metallophilic interactions in the heterobimetallic Ag(I)-Cu(I) acetylide cubane cluster, [Ag₂Cu₂(CCPh)₄(PPh₃)₄]. Single-crystal X-ray diffraction analysis reveals unusually short Ag∙∙∙Ag, Cu∙∙∙Cu, and Ag∙∙∙Cu separations, ranging from 2.5763(9) to 2.9546(8) Å, indicative of strong d¹⁰⋯d¹⁰ argentophilic, cuprophilic, and mixed argento-cuprophilic interactions. Density Functional Theory (DFT) calculations, combined with Electron Localization Function (ELF) analysis, show significant electron localization along these metal–metal contacts, along with electron density delocalization around the silver and copper centers. Quantum Theory of Atoms in Molecules (QTAIM) analysis provides further insight into the electron density at bond critical points (BCP), quantifying the strength of the metallophilic interactions. Additionally, Natural Bond Orbital (NBO) analysis identifies donor–acceptor orbital interactions involved in the Ag∙∙∙Ag, Cu∙∙∙Cu, and Ag∙∙∙Cu contacts, further highlighting the nature of these closed-shell interactions. These combined analyses offer a detailed understanding of the structural, electronic, and photophysical properties of the complex, shedding light on the role of metallophilic interactions in its luminescent behavior.

{"title":"Luminescent tetranuclear Ag(I)/Cu(I) cubane clusters: Investigating argentophilicity, cuprophilicity, and mixed argento-cuprophilicity","authors":"Rais Ahmad Khan , Mohammad H. Jaafar , Arman D. Hadi , Huda Alsaeedi , Ali Alsalme","doi":"10.1016/j.ica.2024.122517","DOIUrl":"10.1016/j.ica.2024.122517","url":null,"abstract":"<div><div>In this article, we have investigated the luminescence properties and metallophilic interactions in the heterobimetallic Ag(I)-Cu(I) acetylide cubane cluster, [Ag2Cu2(C<img>CPh)4(PPh3)4]. Single-crystal X-ray diffraction analysis reveals unusually short Ag∙∙∙Ag, Cu∙∙∙Cu, and Ag∙∙∙Cu separations, ranging from 2.5763(9) to 2.9546(8) Å, indicative of strong d10⋯d10 argentophilic, cuprophilic, and mixed argento-cuprophilic interactions. Density Functional Theory (DFT) calculations, combined with Electron Localization Function (ELF) analysis, show significant electron localization along these metal–metal contacts, along with electron density delocalization around the silver and copper centers. Quantum Theory of Atoms in Molecules (QTAIM) analysis provides further insight into the electron density at bond critical points (BCP), quantifying the strength of the metallophilic interactions. Additionally, Natural Bond Orbital (NBO) analysis identifies donor–acceptor orbital interactions involved in the Ag∙∙∙Ag, Cu∙∙∙Cu, and Ag∙∙∙Cu contacts, further highlighting the nature of these closed-shell interactions. These combined analyses offer a detailed understanding of the structural, electronic, and photophysical properties of the complex, shedding light on the role of metallophilic interactions in its luminescent behavior.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"578 ","pages":"Article 122517"},"PeriodicalIF":2.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143347276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Corrigendum to “Unraveling group dynamics in alkaline electrochemical water splitting using β-substituted porphyrinoids” [Inorganica Chimica Acta 576 (2025) 122453]

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-25 DOI: 10.1016/j.ica.2024.122511

Ishfaq Ahmad Lone, Ravi Kumar

引用次数: 0

Lewis acid catalyzed reaction of dimethyl carbonate with amines: Experimental and theoretical study

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-24 DOI: 10.1016/j.ica.2024.122512

Yakov D. Samuilov, Alexander Y. Samuilov

The effect of various catalysts on the reaction of dimethyl carbonate with aniline leading to the formation of methyl phenylcarbamate was studied. In the absence of catalysts, the interaction practically does not occur. Such Lewis acids as zinc chloride, ferric chloride, exhibit unsatisfactory properties. Zinc and lead acetates have high catalytic properties. The presence of crystalline water in these salts reduces their catalytic activity. In the presence of catalyst, the reaction of aniline with dimethyl carbonate is autocatalytic, which is indicated by the presence of an induction period in it. The induction period disappears if methanol is deliberately introduced into the reaction mixture. A model reaction of dimethyl carbonate with methylamine catalyzed by zinc acetate was studied at the PBE0 and WB97XD levels. The calculation results show that true catalyst is zinc methoxide or zinc oxide.

引用次数: 0

Fe(III)-promoted oxidative dehydrogenation of amines by O2 – Mediated cleavage of C–H bond proceeds via hydrogen atom transfer (HAT)

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-24 DOI: 10.1016/j.ica.2024.122516

Ricardo D. Páez-López , Miguel Á. Gómez-Soto , Héctor F. Cortés-Hernández , Alejandro Solano-Peralta , Miguel Castro , Peter M.H. Kroneck , Martha E. Sosa-Torres

The Fe(III) complex, [Fe^IIIL³]³⁺ (1) (L³, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanonane), is novel because it undergoes an oxidative dehydrogenation reaction in both anoxic (N₂) and oxic (O₂) conditions to form the stable mono-imine Fe(II) complex, [Fe^IIL⁴]²⁺ (2) (L⁴, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanon-1-ene). This process involves the aminyl radical [Fe^II(L³_N•)]²⁺ (2a) and is shown to proceed with a rate-determining step of cleaving the CH bond through the interaction of O₂, with a kinetic isotope effect CH k^CH/k^CD = 2.30. ²H NMR of the deuterated ligand L²-D and product [Fe^IIL⁴-D]²⁺, indicates a regioselective CH cleavage promoted by O₂ through the hydrogen atom transfer (HAT) mechanism, generating HO₂^•. It is also observed that O₂ does not coordinate to the Fe center to form a high-valent Fe oxo species observed in enzymes and their biomimetic complexes. The values for the activation enthalpy ΔH^≠ = 20.38 kcal mol^-1 and the activation entropy ΔS^≠ = −0.018 kcal mol^-1 K⁻¹ fall within the range typically reported for HAT reactions.

{"title":"Fe(III)-promoted oxidative dehydrogenation of amines by O2 – Mediated cleavage of C–H bond proceeds via hydrogen atom transfer (HAT)","authors":"Ricardo D. Páez-López , Miguel Á. Gómez-Soto , Héctor F. Cortés-Hernández , Alejandro Solano-Peralta , Miguel Castro , Peter M.H. Kroneck , Martha E. Sosa-Torres","doi":"10.1016/j.ica.2024.122516","DOIUrl":"10.1016/j.ica.2024.122516","url":null,"abstract":"<div><div>The Fe(III) complex, [FeIIIL3]3+ (1) (L3, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanonane), is novel because it undergoes an oxidative dehydrogenation reaction in both anoxic (N2) and oxic (O2) conditions to form the stable mono-imine Fe(II) complex, [FeIIL4]2+ (2) (L4, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanon-1-ene). This process involves the aminyl radical [FeII(L3N•)]2+ (2a) and is shown to proceed with a rate-determining step of cleaving the C<img>H bond through the interaction of O2, with a kinetic isotope effect C<img>H kCH/kCD = 2.30. 2H NMR of the deuterated ligand L2-D and product [FeIIL4-D]2+, indicates a regioselective C<img>H cleavage promoted by O2 through the hydrogen atom transfer (HAT) mechanism, generating HO2•. It is also observed that O2 does not coordinate to the Fe center to form a high-valent Fe oxo species observed in enzymes and their biomimetic complexes. The values for the activation enthalpy ΔH≠ = 20.38 kcal mol-1 and the activation entropy ΔS≠ = −0.018 kcal mol-1 K−1 fall within the range typically reported for HAT reactions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"578 ","pages":"Article 122516"},"PeriodicalIF":2.7,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143347279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Crystal Structure, spectroscopic investigations (FT-IR, UV/Vis), and DFT/QTAIM/NCI Computations of a novel (η2-hydrogencarbonato) Six-coordinate high-spin Iron(II) picket fence porphyrin complex

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-21 DOI: 10.1016/j.ica.2024.122507

Mondher Dhifet , Bouzid Gassoumi , Jean-Claude Daran , Noureddine Issaoui , Habib Nasri

In this work we have prepared the novel (η²-hydrogencarbonato) high-spin (S = 2) iron(II) picket fence porphyrin ([Fe^II(TpivPP)(η²-HCO₃)]⁻ ion complex (complex I) which was characterized by UV/Vis and IR spectroscopy and single crystal X-ray diffraction molecular structure. These techniques show that the HCO₃⁻ axial ligand is coordinated to the Fe²⁺ metal ion in a bidentate mode and that complex I is high-spin (S = 2). Density functional theory (DFT) calculations were performed on complex I using the DFT/B3LYP/LanL2DZ level of theory to study the HOMO-LUMO shapes and energy, Molecular Electrostatic Potential (MEP) as well as several other global chemical reactivity descriptors in order to evaluate the reactivity of our ferrous η²-hydrogencarbonato porphyrin coordination complex. Furthermore, Quantum Theory of Atoms in Molecules (QTAIM) and Non-Covalent Interaction (NCI) analyses have been performed to study the non-covalent interactions in the crystal lattice of complex I.

{"title":"Crystal Structure, spectroscopic investigations (FT-IR, UV/Vis), and DFT/QTAIM/NCI Computations of a novel (η2-hydrogencarbonato) Six-coordinate high-spin Iron(II) picket fence porphyrin complex","authors":"Mondher Dhifet , Bouzid Gassoumi , Jean-Claude Daran , Noureddine Issaoui , Habib Nasri","doi":"10.1016/j.ica.2024.122507","DOIUrl":"10.1016/j.ica.2024.122507","url":null,"abstract":"<div><div>In this work we have prepared the novel (η2-hydrogencarbonato) high-spin (S = 2) iron(II) picket fence porphyrin ([FeII(TpivPP)(η2-HCO3)]− ion complex (complex I) which was characterized by UV/Vis and IR spectroscopy and single crystal X-ray diffraction molecular structure. These techniques show that the HCO3− axial ligand is coordinated to the Fe2+ metal ion in a bidentate mode and that complex I is high-spin (S = 2). Density functional theory (DFT) calculations were performed on complex I using the DFT/B3LYP/LanL2DZ level of theory to study the HOMO-LUMO shapes and energy, Molecular Electrostatic Potential (MEP) as well as several other global chemical reactivity descriptors in order to evaluate the reactivity of our ferrous η2-hydrogencarbonato porphyrin coordination complex. Furthermore, Quantum Theory of Atoms in Molecules (QTAIM) and Non-Covalent Interaction (NCI) analyses have been performed to study the non-covalent interactions in the crystal lattice of complex I.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122507"},"PeriodicalIF":2.7,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Novel bis-carbacylamidophosphate and its complexes of rare earth elements

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-21 DOI: 10.1016/j.ica.2024.122515

V. Sachok , N. Kariaka , V. Trush , O. Horniichuk , O. Korovin , N. Rusakova , V. Dyakonenko , S. Shishkina , M. Lazarenko , V. Amirkhanov

Considering the unfading interest in lanthanide-based luminescent materials the novel bis-chelating ligand tetramethyl(1,3-phenylenedicarbonyl)-bis-amidophosphate (H₂L) was synthesized. Its coordination ability towards the rare earth elements and the effectivity of sensitization of their luminescence were investigated. X-ray analysis of H₂L points on its chain- like structure created by means of hydrogen bonds NH···OP. The two series of binuclear complexes of rare earth elements Ln₂L₃(H₂O)₂·2H₂O (Ln1) and Ln₂L₃bipy₂·2H₂O (Ln2), where Ln = Eu, Tb, Dy, Y and bipy = 2,2′-bipyridine, were obtained and characterized using elemental and thermal gravimetric analysis, IR, NMR, UV absorption spectroscopy at room temperature and luminescence spectroscopy at 298 and 77 K. The ligand absorbs in the UV region and effectively sensitizes the emission of Eu^III, Tb^III, and Dy^III ions. The complexes of dysprosium emit in visible and NIR regions despite the presence of water molecules in the complexes compositions as well as despite that the enegry gaps between the ligands’ lowest triplet state and the emissive levels of Dy^III are within the range for back energy transfer. The europium and terbium complexes possess bright respectively red and green luminescence with an emission lifetime at room temperature in the range of 1.13–2.60 ms.

{"title":"Novel bis-carbacylamidophosphate and its complexes of rare earth elements","authors":"V. Sachok , N. Kariaka , V. Trush , O. Horniichuk , O. Korovin , N. Rusakova , V. Dyakonenko , S. Shishkina , M. Lazarenko , V. Amirkhanov","doi":"10.1016/j.ica.2024.122515","DOIUrl":"10.1016/j.ica.2024.122515","url":null,"abstract":"<div><div>Considering the unfading interest in lanthanide-based luminescent materials the novel bis-chelating ligand tetramethyl(1,3-phenylenedicarbonyl)-bis-amidophosphate (H2L) was synthesized. Its coordination ability towards the rare earth elements and the effectivity of sensitization of their luminescence were investigated. X-ray analysis of H2L points on its chain- like structure created by means of hydrogen bonds N<img>H···O<img>P. The two series of binuclear complexes of rare earth elements Ln2L3(H2O)2·2H2O (Ln1) and Ln2L3bipy2·2H2O (Ln2), where Ln = Eu, Tb, Dy, Y and bipy = 2,2′-bipyridine, were obtained and characterized using elemental and thermal gravimetric analysis, IR, NMR, UV absorption spectroscopy at room temperature and luminescence spectroscopy at 298 and 77 K. The ligand absorbs in the UV region and effectively sensitizes the emission of EuIII, TbIII, and DyIII ions. The complexes of dysprosium emit in visible and NIR regions despite the presence of water molecules in the complexes compositions as well as despite that the enegry gaps between the ligands’ lowest triplet state and the emissive levels of DyIII are within the range for back energy transfer. The europium and terbium complexes possess bright respectively red and green luminescence with an emission lifetime at room temperature in the range of 1.13–2.60 ms.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122515"},"PeriodicalIF":2.7,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Bimetallic copper complexes of a new amide-based heptadentate N6O ligand: Design, syntheses, structures, and spectroscopic characterization

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-21 DOI: 10.1016/j.ica.2024.122514

Ashley E. Hall , Kraig A. Wheeler , Radu F. Semeniuc

A new dicompartmental N₆O heptadentate ligand has been prepared by linking two bis(pyrazolyl)methane donor groups to a phenol core via amide bridges attached to the 2 and 6 positions of the arene ring. The ligand Bu^t-Ph(OH)–[NH–C(O)–CH(pz)₂]₂ (H₃L, pz = pyrazolyl ring) forms the neutral complexes {Bu^t-Ph(O)–[N–C(O)–CH(pz)₂]₂}[Cu₂(μ-O₂C–CH₃)] (1), and {Bu^t-Ph(O)-[N–C(O)–CH(pz)₂]₂}{Cu₂[μ-O₂C–CH(NI)–CH(CH₃)(CH₂CH₃)]} (2, NI = 1,8-Naphthalimide). These compounds were characterized by ¹H NMR, IR, and UV–Vis spectroscopies, as well as single crystal X-ray diffraction. Their common structural features consist of a triply deprotonated [L]^3- ligand, bridging two copper(II) ions through the phenoxido oxygen atom. The neutrality of the complexes is ensured by the exogenous C(O)O⁻ bridges. As a consequence, the distances between the Cu²⁺ ··· Cu²⁺ ions were found to be about 3.5 Å in both cases. Each copper center is also coordinated by three nitrogen atoms, originating from the deprotonated amide group and the two pyrazolyl rings of the side-arms of the ligand. As such, the geometry around the copper ions can be described as a distorted square pyramid.

{"title":"Bimetallic copper complexes of a new amide-based heptadentate N6O ligand: Design, syntheses, structures, and spectroscopic characterization","authors":"Ashley E. Hall , Kraig A. Wheeler , Radu F. Semeniuc","doi":"10.1016/j.ica.2024.122514","DOIUrl":"10.1016/j.ica.2024.122514","url":null,"abstract":"<div><div>A new dicompartmental N6O heptadentate ligand has been prepared by linking two bis(pyrazolyl)methane donor groups to a phenol core via amide bridges attached to the 2 and 6 positions of the arene ring. The ligand But-Ph(OH)–[NH–C(O)–CH(pz)2]2 (H3L, pz = pyrazolyl ring) forms the neutral complexes {But-Ph(O)–[N–C(O)–CH(pz)2]2}[Cu2(μ-O2C–CH3)] (1), and {But-Ph(O)-[N–C(O)–CH(pz)2]2}{Cu2[μ-O2C–CH(NI)–CH(CH3)(CH2CH3)]} (2, NI = 1,8-Naphthalimide). These compounds were characterized by 1H NMR, IR, and UV–Vis spectroscopies, as well as single crystal X-ray diffraction. Their common structural features consist of a triply deprotonated [L]3- ligand, bridging two copper(II) ions through the phenoxido oxygen atom. The neutrality of the complexes is ensured by the exogenous <img>C(O)O− bridges. As a consequence, the distances between the Cu2+ ··· Cu2+ ions were found to be about 3.5 Å in both cases. Each copper center is also coordinated by three nitrogen atoms, originating from the deprotonated amide group and the two pyrazolyl rings of the side-arms of the ligand. As such, the geometry around the copper ions can be described as a distorted square pyramid.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122514"},"PeriodicalIF":2.7,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138367","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Anionic octahedral halide molybdenum and tungsten clusters with pyrazolate ligands

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-20 DOI: 10.1016/j.ica.2024.122504

Ksenia S. Kozlova , Alexey S. Berezin , Anton A. Ivanov , Michael A. Shestopalov

In this study, we present a convenient and accessible synthesis of [M₆X₈(OCH₃)₆]²⁻ clusters from [M₆X₈X₆]²⁻ (M = Mo, W; X = Br, I) using methanol and sodium hydroxide, without the use of absolute solvents or sodium methylate. The substitution of terminal methylate ligands in the clusters by pyrazolate ligands was conducted using a reaction in the melt of the organic ligand. The formation of anionic [M₆X₈(pz)₆]²⁻ (pz = pyrazolate) complexes was confirmed by both single crystal X-ray diffraction analysis and ¹H NMR spectroscopy in solution. The complexes exhibited broadband emission in solid state with emission maxima ranging from 600 to 700 nm (depending on the cluster core) with quantum yields of approximately 7 %.

引用次数: 0

Binuclear Fe(II) and Cu(II) complexes with 2-(pyridin-2-yl)-1H-benzimidazole and 4,4′-bipyridine: Synthesis, characterization, DFT insights, broad-spectrum bioactivity and docking study

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-12-20 DOI: 10.1016/j.ica.2024.122505

Mai M. Khalaf , Hany M. Abd El-Lateef , Amro Ahmed Taha , Aly Abdou

This study presents the synthesis, structural characterization, theoretical analysis, and biological assessment of two novel binuclear complexes: FeBBNZBIPY and CuBBNZBIPY. These complexes were synthesized from 2-(pyridin-2-yl)-1H-benzimidazole (BBNZ) and 4,4′-bipyridine (BIPY). FT-IR analysis confirmed the bidentate coordination mode of BBNZ and BIPY, while molar conductivity measurements indicated the non-electrolytic nature of both complexes. Structural determination identified FeBBNZBIPY as [Fe₂ (BBNZ)₂(BIPY)(Cl)₆] and CuBBNZBIPY as [Cu₂(BBNZ)₂(BIPY)(Cl)₄(H₂O)₂], both displaying octahedral geometries as verified by spectroscopic analysis. Density functional theory (DFT) calculations provided insights into their electronic properties. Biological assays revealed enhanced anti-inflammatory, antifungal, antibacterial, and antioxidant activities, with CuBBNZBIPY demonstrating superior anti-inflammatory and antioxidant efficacy, showing IC₅₀ values of 90.13 and 72.61 µM, respectively. Molecular docking studies further highlighted specific protein interactions, with CuBBNZBIPY exhibiting high binding energies of −8.71, −8.79, −8.92, and −8.92 kcal/mol against targets 5iq9, 6CLV, 5IJT, and 5IKT, respectively, underscoring the therapeutic potential of these complexes across various biomedical applications.

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