Pub Date : 2024-08-10DOI: 10.1016/j.ica.2024.122313
Seeing the frontier molecular orbitals (FMO) picture of β-d-glucopyranose–silver+ (1:1) complex ([Ag(C6H12O6)]+) reported in a recent article (Mondal, 2024) [53], we used the FMO based approach to obtain inverted sandwich like organometallic complex comprising X3 (X=Be, Mg) core, in silico. Thermodynamic feasibility of obtaining [(C6H12O6)Ag-X3-Ag(C6H12O6)] (X=Be, Mg) complexes are explored. Conceptual density functional theory (CDFT) based reactivity descriptors guide to ascertain the stability order of such complexes. By the help of natural bond orbital analysis, Wiberg bond indices (WBI), bond critical point analysis, electron density descriptors, and gradient isosurface between selected contacts, the nature of interaction between the X3 core and Ag metals are studied. FMO of the complexes further help in ascertaining the nature of binding. Energy decomposition analysis marks the interaction between X3 and Ag metals in [(C6H12O6)Ag-X3-Ag(C6H12O6)] (X=Be, Mg) as partially covalent. Negative values of nucleus independent chemical shift (NICS) at the triangular ring (X3) centres [NICS(0)] indicate aromatic property.
看到最近一篇文章(Mondal, 2024)[53]中报道的β-d-吡喃葡萄糖-银+(1:1)复合物([Ag(C6H12O6)]+)的前沿分子轨道(FMO)图,我们利用基于 FMO 的方法,在硅学中获得了以 X3(X=Be、Mg)为核心的倒三明治状有机金属复合物。我们探讨了获得[(C6H12O6)Ag-X3-Ag(C6H12O6)](X=Be、Mg)复合物的热力学可行性。基于概念密度泛函理论(CDFT)的反应性描述符为确定此类配合物的稳定顺序提供了指导。通过自然键轨道分析、维伯格键指数 (WBI)、键临界点分析、电子密度描述符以及选定接触点之间的梯度等值面,研究了 X3 核心与 Ag 金属之间相互作用的性质。复合物的 FMO 进一步帮助确定了结合的性质。能量分解分析表明,[(C6H12O6)Ag-X3-Ag(C6H12O6)] (X=Be、Mg)中 X3 与 Ag 金属的相互作用为部分共价。三角环(X3)中心[NICS(0)]的核独立化学位移(NICS)为负值,表明其具有芳香特性。
{"title":"β-d-Glucopyranose – Silver+ (1:1) complex assisted aromaticity involving electron deficient X3 (X=Be, Mg) core","authors":"","doi":"10.1016/j.ica.2024.122313","DOIUrl":"10.1016/j.ica.2024.122313","url":null,"abstract":"<div><p>Seeing the frontier molecular orbitals (FMO) picture of β-<span>d</span>-glucopyranose–silver+ (1:1) complex ([Ag(C<sub>6</sub>H<sub>12</sub>O<sub>6</sub>)]<sup>+</sup>) reported in a recent article (Mondal, 2024) [53], we used the FMO based approach to obtain inverted sandwich like organometallic complex comprising X<sub>3</sub> (X=Be, Mg) core, <em>in silico</em>. Thermodynamic feasibility of obtaining [(C<sub>6</sub>H<sub>12</sub>O<sub>6</sub>)Ag-X<sub>3</sub>-Ag(C<sub>6</sub>H<sub>12</sub>O<sub>6</sub>)] (X=Be, Mg) complexes are explored. Conceptual density functional theory (CDFT) based reactivity descriptors guide to ascertain the stability order of such complexes. By the help of natural bond orbital analysis, Wiberg bond indices (WBI), bond critical point analysis, electron density descriptors, and gradient isosurface between selected contacts, the nature of interaction between the X<sub>3</sub> core and Ag metals are studied. FMO of the complexes further help in ascertaining the nature of binding. Energy decomposition analysis marks the interaction between X<sub>3</sub> and Ag metals in [(C<sub>6</sub>H<sub>12</sub>O<sub>6</sub>)Ag-X<sub>3</sub>-Ag(C<sub>6</sub>H<sub>12</sub>O<sub>6</sub>)] (X=Be, Mg) as partially covalent. Negative values of nucleus independent chemical shift (NICS) at the triangular ring (X<sub>3</sub>) centres [NICS(0)] indicate aromatic property.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141992677","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}
Pub Date : 2024-08-10DOI: 10.1016/j.ica.2024.122305
The synthesis of original 6-(azol-1-yl)phenanthridine ligands and a copper(II) complex based on them is reported. Comprehensive studies of the structural, physicochemical, and electrocatalytic properties for the selected 6-(1H-pyrazol-1-yl)phenanthridine-containing coordination compound have been carried out. The latter has demonstrated pronounced electrochemical and electrocatalytic activities in the enzyme-free cholesterol oxidation in DMSO. A six-stage mechanism including electrocatalytic reduction of cholesterol and subsequent oxidation of its reduction products has been proposed and underpinned by quantum mechanical considerations. Obtained analytical characteristics of the enzyme-free cholesterol oxidation (LoD 0.0032 mM, detectable concentrations 0.01–0.40 mM) open a prospect towards the investigated complexes to be applied as sensitive elements of portable electrochemical platforms for the point-of-care diagnostics.
{"title":"Azolylphenanthridine-ligated Cu(II) catalyst for electrochemical oxidation of cholesterol in aprotic medium","authors":"","doi":"10.1016/j.ica.2024.122305","DOIUrl":"10.1016/j.ica.2024.122305","url":null,"abstract":"<div><p>The synthesis of original 6-(azol-1-yl)phenanthridine ligands and a copper(II) complex based on them is reported. Comprehensive studies of the structural, physicochemical, and electrocatalytic properties for the selected 6-(1<em>H</em>-pyrazol-1-yl)phenanthridine-containing coordination compound have been carried out. The latter has demonstrated pronounced electrochemical and electrocatalytic activities in the enzyme-free cholesterol oxidation in DMSO. A six-stage mechanism including electrocatalytic reduction of cholesterol and subsequent oxidation of its reduction products has been proposed and underpinned by quantum mechanical considerations. Obtained analytical characteristics of the enzyme-free cholesterol oxidation (LoD 0.0032 mM, detectable concentrations 0.01–0.40 mM) open a prospect towards the investigated complexes to be applied as sensitive elements of portable electrochemical platforms for the point-of-care diagnostics.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142006342","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}
Pub Date : 2024-08-09DOI: 10.1016/j.ica.2024.122301
The depletion of traditional fossil fuels, as well as the increase in global energy demand, is currently driving the need for sustainable energy solutions. The primary challenge in the practical application of hydrogen fuel cells is to reduce or replace the use of platinum material in the electrode catalysts. In this work, by using density functional theory (DFT) we investigate the oxygen reduction reaction of Ag-based core-shell nanoclusters with 12 different 3d-5d transition metal (TM) cores (groups 8–11). The stability is assessed by calculating the binding, excess and segregation energies, indicating that the most stable mixing is found in the noble metal-encapsulated structures, such as Pd@Ag, Pt@Ag, Rh@Ag and Ir@Ag particles. The reaction barrier for OH formation is found to be the limiting step with values ranging from 0.59 to 1.36 eV among the core-shell Ag-based nanoclusters, which are comparable with the energy barrier of the Pt(111) surface (0.97 eV). However, the correlation of the d-band center and activation barriers indicate that Ru@Ag, Rh@Ag, and Os@Ag mixings are the most suitable for the oxygen reduction reaction. These results indicate that small Ag-based core-shell nanoclusters with transition metal cores are active for the ORR application in alkaline media.
{"title":"First principles study for Ag-based core-shell nanoclusters with 3d-5d transition metal cores for the oxygen reduction reaction","authors":"","doi":"10.1016/j.ica.2024.122301","DOIUrl":"10.1016/j.ica.2024.122301","url":null,"abstract":"<div><p>The depletion of traditional fossil fuels, as well as the increase in global energy demand, is currently driving the need for sustainable energy solutions. The primary challenge in the practical application of hydrogen fuel cells is to reduce or replace the use of platinum material in the electrode catalysts. In this work, by using density functional theory (DFT) we investigate the oxygen reduction reaction of Ag-based core-shell nanoclusters with 12 different 3d-5d transition metal (TM) cores (groups 8–11). The stability is assessed by calculating the binding, excess and segregation energies, indicating that the most stable mixing is found in the noble metal-encapsulated structures, such as Pd@Ag, Pt@Ag, Rh@Ag and Ir@Ag particles. The reaction barrier for OH formation is found to be the limiting step with values ranging from 0.59 to 1.36 eV among the core-shell Ag-based nanoclusters, which are comparable with the energy barrier of the Pt(111) surface (0.97 eV). However, the correlation of the d-band center and activation barriers indicate that Ru@Ag, Rh@Ag, and Os@Ag mixings are the most suitable for the oxygen reduction reaction. These results indicate that small Ag-based core-shell nanoclusters with transition metal cores are active for the ORR application in alkaline media.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141990354","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}
Pub Date : 2024-08-08DOI: 10.1016/j.ica.2024.122304
This review centres on the synthesis of zirconium(IV) complexes using Schiff base ligands. The first section provides a brief introduction to Schiff bases and zirconium(IV) complexes. In the second section, the synthesis of Schiff base zirconium(IV) complexes is explored through literature spanning from 2001 to 2022. The most important third section is divided into four subsections covering these complexes’ physical, spectroscopic, X-ray, and thermal studies. The fourth section summarizes the broad range of remarkable catalytic (polymerization and condensation) and biological (antibacterial, antifungal, anti-inflammatory, larvicidal) properties exhibited by Schiff base zirconium(IV) complexes.
{"title":"Multidentate unsymmetrically substituted Schiff bases zirconium(IV) complexes: Synthesis, characterization, X-ray, thermal studies, catalytical, and biological application (A survey of literature from 2001 to 2022)","authors":"","doi":"10.1016/j.ica.2024.122304","DOIUrl":"10.1016/j.ica.2024.122304","url":null,"abstract":"<div><p>This review centres on the synthesis of zirconium(IV) complexes using Schiff base ligands. The first section provides a brief introduction to Schiff bases and zirconium(IV) complexes. In the second section, the synthesis of Schiff base zirconium(IV) complexes is explored through literature spanning from 2001 to 2022. The most important third section is divided into four subsections covering these complexes’ physical, spectroscopic, X-ray, and thermal studies. The fourth section summarizes the broad range of remarkable catalytic (polymerization and condensation) and biological (antibacterial, antifungal, anti-inflammatory, larvicidal) properties exhibited by Schiff base zirconium(IV) complexes.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141979225","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}
Pub Date : 2024-08-08DOI: 10.1016/j.ica.2024.122310
Acetate complexes of rare earth elements are extensively studied compounds known for their diverse properties and potential applications and lanthanum acetate hydrate is commercially available. In this work, a powdered anhydrous lanthanum acetate (La(CH3COO)3) sample was prepared by dissolving lanthanum oxide (La2O3) in an excess of acetic acid (CH3COOH) and distilled water (H2O), followed by direct evaporation at 150 °C. The decomposition of La(CH3COO)3 was studied, showing initiation around 300 °C and conclusion at ≥700 °C, with four distinct thermal events (I–IV) of mass loss. Gas phase identification revealed acetone and carbon dioxide as decomposition products, indicating pyrolytic decarboxylation. The final thermal effect (IV) is linked to the decomposition of La2O2CO3 to La2O3. The DFT refinement of atomic coordinates of hydrogen atoms, which were unavailable from experiment, was successfully performed. Obtained structural data was checked using vibrational spectroscopy method. The calculated electronic band structure of La(CH3COO)3 indicates it as an indirect wide band gap material with values of direct transition close to indirect. The optical bandgap is found to be 5.49 eV, suggesting that the charge transfer in La(CH3COO)3 can be optically activated with wavelengths shorter than 226 nm, which falls within the deep UV (DUV) region.
稀土元素的醋酸盐络合物因其多种多样的特性和潜在应用而被广泛研究,醋酸镧水合物可在市场上买到。在这项工作中,通过将氧化镧(La2O3)溶解在过量的醋酸(CH3COOH)和蒸馏水(H2O)中,然后在 150 °C 下直接蒸发,制备出了粉末状无水醋酸镧(La(CH3COO)3)样品。研究表明,La(CH3COO)3 的分解过程在 300 °C 左右开始,在 ≥700 °C 时结束,有四个不同的质量损失热事件(I-IV)。气相鉴定显示分解产物为丙酮和二氧化碳,表明发生了热解脱羧反应。最后的热效应(IV)与 La2O2CO3 分解为 La2O3 有关。实验中无法获得的氢原子的原子坐标已成功地进行了 DFT 精炼。利用振动光谱法对所获得的结构数据进行了检验。计算得出的 La(CH3COO)3 电子能带结构表明,它是一种间接宽带隙材料,直接转变值接近间接值。光带隙为 5.49 eV,这表明 La(CH3COO)3 中的电荷转移可以在波长短于 226 nm(属于深紫外(DUV)区域)的条件下被光学激活。
{"title":"Synthesis of anhydrous lanthanum acetate. Analysis of it’s structural, thermal and electronic properties","authors":"","doi":"10.1016/j.ica.2024.122310","DOIUrl":"10.1016/j.ica.2024.122310","url":null,"abstract":"<div><p>Acetate complexes of rare earth elements are extensively studied compounds known for their diverse properties and potential applications and lanthanum acetate hydrate is commercially available. In this work, a powdered anhydrous lanthanum acetate (La(CH<sub>3</sub>COO)<sub>3</sub>) sample was prepared by dissolving lanthanum oxide (La<sub>2</sub>O<sub>3</sub>) in an excess of acetic acid (CH<sub>3</sub>COOH) and distilled water (H<sub>2</sub>O), followed by direct evaporation at 150 °C. The decomposition of La(CH<sub>3</sub>COO)<sub>3</sub> was studied, showing initiation around 300 °C and conclusion at ≥700 °C, with four distinct thermal events (I–IV) of mass loss. Gas phase identification revealed acetone and carbon dioxide as decomposition products, indicating pyrolytic decarboxylation. The final thermal effect (IV) is linked to the decomposition of La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> to La<sub>2</sub>O<sub>3</sub>. The DFT refinement of atomic coordinates of hydrogen atoms, which were unavailable from experiment, was successfully performed. Obtained structural data was checked using vibrational spectroscopy method. The calculated electronic band structure of La(CH<sub>3</sub>COO)<sub>3</sub> indicates it as an indirect wide band gap material with values of direct transition close to indirect. The optical bandgap is found to be 5.49 eV, suggesting that the charge transfer in La(CH<sub>3</sub>COO)<sub>3</sub> can be optically activated with wavelengths shorter than 226 nm, which falls within the deep UV (DUV) region.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141979224","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}
Pub Date : 2024-08-08DOI: 10.1016/j.ica.2024.122306
Highly luminescent octa-coordinated samarium(III) complexes including [Sm(TFDH)3(Bpy)] (Sm1), [Sm(TFDH)3(S1)] (Sm2), [Sm(TFDH)3(S2)] (Sm3) and [Sm(TFDH)3(S3)] (Sm4) were synthesized utilizing fluorinated β-diketone i.e. 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (TFDH) and bidentate auxiliary ligands. Here, S1 is 5,5ʹ-dibromo-2,2′-bipyridine; S2 is 5-bromo-5ʹ-(3,4-(ethylenedioxy)thien-2-yl)2,2′-bipyridine and S3 is 5,5′-bis(3,4-(ethylenedioxy)thien-2-yl)2,2′-bipyridine. Different properties of prepared complexes were examined using numerous characterization techniques such as elemental, FT-IR, 1H NMR, absorption and thermogravimetric analyses. Nuclear magnetic resonance (NMR) data affirms the coordination of three TFDH units and one bidentate ligand with metal ion in each complex. Sm(III) complexes exhibit thermal stability up to 250 °C when subjected to an inert atmosphere composed of nitrogen (N2) gas. The luminescent characteristics of the powdered Sm1-Sm4 complexes were also investigated. Each complex displays distinct peaks at around 564, 605, 648 and 707 nm in their emission profiles. The orange-red emission of these complexes was observed via colorimetry which strongly aligns with the highly intense peak observed at 648 nm (4G5/2→6H9/2). The strong luminosity and color coordinates suggest that the complexes could serve as potential candidates for use in OLEDs and display panel.
{"title":"Synthesis and photoluminescent studies of orange–red emissive samarium(III) complexes with 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and 2,2′-bipyridine and its distinctive analogous","authors":"","doi":"10.1016/j.ica.2024.122306","DOIUrl":"10.1016/j.ica.2024.122306","url":null,"abstract":"<div><p>Highly luminescent octa-coordinated samarium(III) complexes including [Sm(TFDH)<sub>3</sub>(Bpy)] (Sm1), [Sm(TFDH)<sub>3</sub>(S<sub>1</sub>)] (Sm2), [Sm(TFDH)<sub>3</sub>(S<sub>2</sub>)] (Sm3) and [Sm(TFDH)<sub>3</sub>(S<sub>3</sub>)] (Sm4) were synthesized utilizing fluorinated β-diketone <em>i.e.</em> 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (TFDH) and bidentate auxiliary ligands. Here, S<sub>1</sub> is 5,5ʹ-dibromo-2,2′-bipyridine; S<sub>2</sub> is 5-bromo-5ʹ-(3,4-(ethylenedioxy)thien-2-yl)2,2′-bipyridine and S<sub>3</sub> is 5,5′-bis(3,4-(ethylenedioxy)thien-2-yl)2,2′-bipyridine. Different properties of prepared complexes were examined using numerous characterization techniques such as elemental, FT-IR, <sup>1</sup>H NMR, absorption and thermogravimetric analyses. Nuclear magnetic resonance (NMR) data affirms the coordination of three TFDH units and one bidentate ligand with metal ion in each complex. Sm(III) complexes exhibit thermal stability up to 250 °C when subjected to an inert atmosphere composed of nitrogen (N<sub>2</sub>) gas. The luminescent characteristics of the powdered Sm1-Sm4 complexes were also investigated. Each complex displays distinct peaks at around 564, 605, 648 and 707 nm in their emission profiles. The orange-red emission of these complexes was observed <em>via</em> colorimetry which strongly aligns with the highly intense peak observed at 648 nm (<sup>4</sup>G<sub>5/2</sub>→<sup>6</sup>H<sub>9/2</sub>). The strong luminosity and color coordinates suggest that the complexes could serve as potential candidates for use in OLEDs and display panel.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141964175","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}
Pub Date : 2024-08-06DOI: 10.1016/j.ica.2024.122286
Owing to the biological importance of copper(II) coordination complexes, herein, a new mononuclear complex, [Cu(Eta)2(CNBz)2], where CNBz = 4-chloro-3-nitrobenzoate, Eta = ethanolamine, was isolated using an appropriate stoichiometric ratio of reactants under ambient reaction conditions. The newly synthesized complex was substantiated by applying various analytical methods such as elemental analysis, and FT-IR. The complex crystallized in monoclinic crystal system with P21/n space group. Single X-ray crystal structure elucidation delineate the formation of layer by layer fashion of complex molecules which was further stabilized by multitude of non-covalent ineteractions especially hydrogen bonding. The quantitative estimation of these interactions was carried out using Hirshfeld surface analysis and theoretical calculations. The potential antibacterial activity of the complex was demonstrated by in-vitro and in-silico antibacterial experiments. The attained significant results delineate the crucial role of various functionalities in the complex in rendering interactions with various amino acid units in the protein thereby influencing the biological activities. In nutshell, coordination complexes, when ligands employed were endowed with various donor and acceptor functional groups will influence the lattice stabilization as well as biological efficacy of such complexes.
{"title":"Supramolecular self assembly in [Cu(ethanolamine)2(4-chloro-3-nitrobenzoate)2]: Synthesis, structural Characterization, theoretical Investigations, in-vitro and in-silico- antibacterial analyses","authors":"","doi":"10.1016/j.ica.2024.122286","DOIUrl":"10.1016/j.ica.2024.122286","url":null,"abstract":"<div><p>Owing to the biological importance of copper(II) coordination complexes, herein, a new mononuclear complex, [Cu(Eta)<sub>2</sub>(CNBz)<sub>2</sub>], where CNBz = 4-chloro-3-nitrobenzoate, Eta = ethanolamine, was isolated using an appropriate stoichiometric ratio of reactants under ambient reaction conditions. The newly synthesized complex was substantiated by applying various analytical methods such as elemental analysis, and FT-IR. The complex crystallized in monoclinic crystal system with <em>P</em>2<sub>1</sub>/<em>n</em> space group. Single X-ray crystal structure elucidation delineate the formation of layer by layer fashion of complex molecules which was further stabilized by multitude of non-covalent ineteractions especially hydrogen bonding. The quantitative estimation of these interactions was carried out using Hirshfeld surface analysis and theoretical calculations. The potential antibacterial activity of the complex was demonstrated by <em>in-vitro</em> and <em>in-silico</em> antibacterial experiments. The attained significant results delineate the crucial role of various functionalities in the complex in rendering interactions with various amino acid units in the protein thereby influencing the biological activities. In nutshell, coordination complexes, when ligands employed were endowed with various donor and acceptor functional groups will influence the lattice stabilization as well as biological efficacy of such complexes.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141963554","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}
Pub Date : 2024-08-04DOI: 10.1016/j.ica.2024.122298
Two imidazolidine grafted Schiff bases H3L2 and H3L3 have been utilized to fasten the Cu2 core in four new complexes [Cu2(μ-L2)(μ-O2CMe)]·H2O (1·H2O), [Cu2(μ-L2)(μ-O2COMe)]·H2O (2·H2O), [Cu2(μ-L2)(μ-NO3)]·H2O (3·H2O) and [Cu2L3(μ-OAc)]·5H2O (4·5H2O). Room temperature solution reaction of H3L2 with Cu2(OAc)4·2H2O provided 1·H2O in good yield. Follow-up reaction of 1·H2O with Et4NOH in air replaces μ-O2CMe (acetato) bridge by MeOCO2− (monomethyl carbonato) linker in 2·H2O. Single crystal X-ray structure established the individual complexes and confirmed the fixation of atmospheric CO2. Variable temperature (2 to 300 K) magnetic susceptibility measurements recognized the antiferromagnetic exchange interactions between the adjacent copper(II) centers in complexes 2 and 3. The amount of spin–spin interactions are found to be higher for ancillary NO3− bridge (−284 cm−1) compared to the in situ transformed MeOCO2− bridged (−1.64 cm−1).
{"title":"Facile synthesis of imidazolidinyl phenolate supported Dicopper(II/II) Complexes: Activation and fixation of atmospheric CO2 as MeOCO2− showing exogenous bridge modulating magnetic exchange coupling","authors":"","doi":"10.1016/j.ica.2024.122298","DOIUrl":"10.1016/j.ica.2024.122298","url":null,"abstract":"<div><p>Two imidazolidine grafted Schiff bases H<sub>3</sub>L<sub>2</sub> and H<sub>3</sub>L<sub>3</sub> have been utilized to fasten the Cu<sub>2</sub> core in four new complexes [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>CMe)]·H<sub>2</sub>O (<strong>1</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>COMe)]·H<sub>2</sub>O (<strong>2</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-NO<sub>3</sub>)]·H<sub>2</sub>O (<strong>3</strong>·H<sub>2</sub>O) and [Cu<sub>2</sub>L<sub>3</sub>(<em>μ</em>-OAc)]·5H<sub>2</sub>O (<strong>4</strong>·5H<sub>2</sub>O). Room temperature solution reaction of H<sub>3</sub>L<sub>2</sub> with Cu<sub>2</sub>(OAc)<sub>4</sub>·2H<sub>2</sub>O provided <strong>1</strong>·H<sub>2</sub>O in good yield. Follow-up reaction of <strong>1</strong>·H<sub>2</sub>O with Et<sub>4</sub>NOH in air replaces <em>μ</em>-O<sub>2</sub>CMe (acetato) bridge by MeOCO<sub>2</sub><sup>−</sup> (monomethyl carbonato) linker in <strong>2</strong>·H<sub>2</sub>O. Single crystal X-ray structure established the individual complexes and confirmed the fixation of atmospheric CO<sub>2</sub>. Variable temperature (2 to 300 K) magnetic susceptibility measurements recognized the antiferromagnetic exchange interactions between the adjacent copper(II) centers in complexes <strong>2</strong> and <strong>3</strong>. The amount of spin–spin interactions are found to be higher for ancillary NO<sub>3</sub><sup>−</sup> bridge (−284 <!--> <!-->cm<sup>−1</sup>) compared to the <em>in situ</em> transformed MeOCO<sub>2</sub><sup>−</sup> bridged (−1.64 <!--> <!-->cm<sup>−1</sup>).</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141963144","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}
Pub Date : 2024-08-03DOI: 10.1016/j.ica.2024.122295
In this review article, we present a brief survey of the recent contributions (2018–2024) appeared in the scientific literature, describing the use of the cage-like water-soluble monodentate phosphine 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (also known as 1,3,5-triaza-7-phosphadamantane, PTA), some of its derivatives and a higher homologue as stabilizing ligands for precious and non-precious metal complexes, with various applications in homogeneous catalytic processes in water and biphasic media.
{"title":"Catalytic reactions promoted by metal complexes stabilized by 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (PTA) and derivatives. A brief survey of recent results","authors":"","doi":"10.1016/j.ica.2024.122295","DOIUrl":"10.1016/j.ica.2024.122295","url":null,"abstract":"<div><p>In this review article, we present a brief survey of the recent contributions (2018–2024) appeared in the scientific literature, describing the use of the cage-like water-soluble monodentate phosphine 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (also known as 1,3,5-triaza-7-phosphadamantane, PTA), some of its derivatives and a higher homologue as stabilizing ligands for precious and non-precious metal complexes, with various applications in homogeneous catalytic processes in water and biphasic media.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324003864/pdfft?md5=9606090ff8d8449a886c73ec0c1640ec&pid=1-s2.0-S0020169324003864-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141963143","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}
Pub Date : 2024-08-03DOI: 10.1016/j.ica.2024.122296
Two coordination polymers (CPs), [Cd3(L)3(phen)2]n (1) and [Mn(L)(phen)]n (2), [H3L=3,3′-(1,4-phenylenebis(methylenoxy)dibezoic acid] were synthesized via hydrothermal method. 1 features a 2D layered structure with the potential for 3D network formation through weak interactions, 2 exhibits a 1D waved chain capable of forming 3D polymeric chains via intra- or intermolecular hydrogen bonding (OH···O) interactions. Both CPs demonstrate promising photocatalytic activity against antibiotics, including chloramphenicol (CAP), metronidazole (MDZ), nitrofurazone (NFZ), oxytetracycline (OXY), and sulfamethazine (SMZ). Notably, CP 1 shows superior photocatalytic activity for NFZ degradation. Systematic investigations revealed that under optimized conditions, CP 1 achieves a remarkable ∼ 92.21 % photodegradation of NFZ at a concentration of 40 ppm NFZ with a photocatalyst dosage of 25 mg/L within 50 min. Radical quencher experiments identified h+ (positive holes) and O2•- as the primary active species driving the photodegradation process. Additionally, CP 1 maintained consistent performance over five cycles, indicating its stability and reusability for NFZ degradation.
{"title":"Two new transition CdII and MnII-based MOFs for highly effective photodegradation antibiotics","authors":"","doi":"10.1016/j.ica.2024.122296","DOIUrl":"10.1016/j.ica.2024.122296","url":null,"abstract":"<div><p>Two coordination polymers (CPs), [Cd<sub>3</sub>(L)<sub>3</sub>(phen)<sub>2</sub>]<sub>n</sub> (<strong>1</strong>) and [Mn(L)(phen)]<sub>n</sub> (<strong>2</strong>), [H<sub>3</sub>L=3,3′-(1,4-phenylenebis(methylenoxy)dibezoic acid] were synthesized <em>via</em> hydrothermal method. <strong>1</strong> features a 2D layered structure with the potential for 3D network formation through weak interactions, <strong>2</strong> exhibits a 1D waved chain capable of forming 3D polymeric chains <em>via</em> intra- or intermolecular hydrogen bonding (O<img>H···O) interactions. Both CPs demonstrate promising photocatalytic activity against antibiotics, including chloramphenicol (CAP), metronidazole (MDZ), nitrofurazone (NFZ), oxytetracycline (OXY), and sulfamethazine (SMZ). Notably, <strong>CP 1</strong> shows superior photocatalytic activity for NFZ degradation. Systematic investigations revealed that under optimized conditions, <strong>CP 1</strong> achieves a remarkable ∼ 92.21 % photodegradation of NFZ at a concentration of 40 ppm NFZ with a photocatalyst dosage of 25 mg/L within 50 min. Radical quencher experiments identified h<sup>+</sup> (positive holes) and O<sub>2</sub><sup>•-</sup> as the primary active species driving the photodegradation process. Additionally, <strong>CP 1</strong> maintained consistent performance over five cycles, indicating its stability and reusability for NFZ degradation.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141961709","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}