Pub Date : 2024-09-12DOI: 10.1016/j.ica.2024.122381
The rapid detection of pollutants in the environment is of great significance. In this work, a novel MOF, namely [Zn(TPPA)(L)]n (1) has been synthesized based on a π-electron rich triangular ligand TPPA (TPPA=tris(4-(pyridin-4-yl)phenyl)amine and H2L=2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid). Compound 1 is a 3-fold interpenetrating (3,5)-connected 3D framework. Photoluminescence studies indicate that the emission of 1 result from the charge transfer transition between ligands (π → π*). 1 with excellent luminous performance can be applied as a multi-functional chemical sensor for nitroaromatic compounds (NACs), toxic metal ions and antibiotics, and quick response. In addition, 1 exhibits photocatalytic activity for the degradation of methyl orange (MO) in the visible regions and is stable during the photocatalysis process. The effective detection of NACs and antibiotics was rationalized by density functional theory (DFT) calculation of the energy bands of NACs and antibiotics, which revealed that photoinduced electron transfer (PET) mechanism is largely responsible for the sensing of NACs. PET mechanism and resonance energy transfer play significant roles in the exclusive sensing of tetracycline hydrochloride (TCH).
{"title":"A novel Zn MOFs as a multifunctional sensitive chemical sensor for the rapid detection of nitroaromatic compounds, Tetracycline, Fe3+, and degradation for methyl orange","authors":"","doi":"10.1016/j.ica.2024.122381","DOIUrl":"10.1016/j.ica.2024.122381","url":null,"abstract":"<div><p>The rapid detection of pollutants in the environment is of great significance. In this work, a novel MOF, namely [Zn(TPPA)(L)]<sub>n</sub> (1) has been synthesized based on a π-electron rich triangular ligand TPPA (TPPA=tris(4-(pyridin-4-yl)phenyl)amine and H<sub>2</sub>L=2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid). Compound 1 is a 3-fold interpenetrating (3,5)-connected 3D framework. Photoluminescence studies indicate that the emission of 1 result from the charge transfer transition between ligands (π → π*). 1 with excellent luminous performance can be applied as a multi-functional chemical sensor for nitroaromatic compounds (NACs), toxic metal ions and antibiotics, and quick response. In addition, 1 exhibits photocatalytic activity for the degradation of methyl orange (MO) in the visible regions and is stable during the photocatalysis process. The effective detection of NACs and antibiotics was rationalized by density functional theory (DFT) calculation of the energy bands of NACs and antibiotics, which revealed that photoinduced electron transfer (PET) mechanism is largely responsible for the sensing of NACs. PET mechanism and resonance energy transfer play significant roles in the exclusive sensing of tetracycline hydrochloride (TCH).</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004729/pdfft?md5=d5257d8ada8aba2e64634703f8aa15ce&pid=1-s2.0-S0020169324004729-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241445","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 : 2024-09-10DOI: 10.1016/j.ica.2024.122371
Rare homoleptic divalent chromium complexes have been isolated by reacting two equivalents of sterically bulky deprotonated 2–aminopyridine ligands, N–(2,4,6–trimethylphenyl)–[6–(2,4,6–trimethylphenyl)–pyridine–2–yl]–amine (1), N–(2,6–diisopropylphenyl)–[6–(2,6–dimethylphenyl)–pyridine–2–yl]–amine (2) and N–(2,6–diisopropylphenyl)–[6–(2,4,6–trimethylphenyl)–pyridine–2–yl]–amine (3) with CrCl2 in tetrahydrofuran (THF). Reaction of deprotonated 1 proceeds smoothly at room temperature while that of sterically more bulky 2 and 3 at reflux temperature. The respective bis(aminopyridinate) Cr complexes (4–6) are monomeric and show different orientations of the coordinated ligands. For compound 5, two isomers were identified. For 4 and 5a the two ligands show head to tail arrangement while in 5b and 6 the two ligands adopt the unknown head to head arrangement of aminopyridinato ligands. All the complexes show distorted square planar geometries around the chromium center. For 4 and 5a in which the ligands are coordinated in transoid manner the pyridine rings and amido nitrogen atom lie in the coordination plane of chromium. Hirshfeld analyses showed that H∙∙∙H and H∙∙∙C/C∙∙∙H π–interactions were the main and at times the strongest contributions for the intermolecular interactions.
{"title":"Homoleptic chromium(II) aminopyridinates: Transoid vs cisoid coordination","authors":"","doi":"10.1016/j.ica.2024.122371","DOIUrl":"10.1016/j.ica.2024.122371","url":null,"abstract":"<div><p>Rare homoleptic divalent chromium complexes have been isolated by reacting two equivalents of sterically bulky deprotonated 2–aminopyridine ligands, N–(2,4,6–trimethylphenyl)–[6–(2,4,6–trimethylphenyl)–pyridine–2–yl]–amine (<strong>1</strong>), N–(2,6–diisopropylphenyl)–[6–(2,6–dimethylphenyl)–pyridine–2–yl]–amine (<strong>2</strong>) and N–(2,6–diisopropylphenyl)–[6–(2,4,6–trimethylphenyl)–pyridine–2–yl]–amine (<strong>3</strong>) with CrCl<sub>2</sub> in tetrahydrofuran (THF). Reaction of deprotonated <strong>1</strong> proceeds smoothly at room temperature while that of sterically more bulky <strong>2</strong> and <strong>3</strong> at reflux temperature. The respective bis(aminopyridinate) Cr complexes (<strong>4</strong>–<strong>6</strong>) are monomeric and show different orientations of the coordinated ligands. For compound <strong>5</strong>, two isomers were identified. For <strong>4</strong> and <strong>5a</strong> the two ligands show head to tail arrangement while in <strong>5b</strong> and <strong>6</strong> the two ligands adopt the unknown head to head arrangement of aminopyridinato ligands. All the complexes show distorted square planar geometries around the chromium center. For <strong>4</strong> and <strong>5a</strong> in which the ligands are coordinated in transoid manner the pyridine rings and amido nitrogen atom lie in the coordination plane of chromium. Hirshfeld analyses showed that H∙∙∙H and H∙∙∙C/C∙∙∙H π–interactions were the main and at times the strongest contributions for the intermolecular interactions.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004626/pdfft?md5=ece4ab73bbe1547047cb671dbb544b91&pid=1-s2.0-S0020169324004626-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241448","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 : 2024-09-10DOI: 10.1016/j.ica.2024.122374
In this work, we have synthesized six coordination polymers using the organic ligand 3-carboxy-1-(3′-carboxybenzyl)-2-oxidopyridinium (H2L). The compounds, named [Co(L)(H2O)2]n (1), [Co(L)(2,2′-bpy)(H2O)]n (2), [Co(L)(4,4′-bpy)0.5]n (3), [Mn2(L)2(H2O)2]n (4), [Mn(L)(2,2′-bpy)(H2O)]n (5) and [Mn(L)(phen)(H2O)]n (6), where 2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine and phen = 1,10-phenanthroline, were prepared under hydrothermal conditions and characterized using various physical measurements. The single-crystal X-ray diffraction analyses show that compounds 1–6 possess different structures because of multiple coordination modes and weak interactions. The Hirshfeld surface analyses of compounds 1–6 have also been studied in detail.
{"title":"Six new coordination polymers based on 3-carboxy-1-(3′-carboxybenzyl)-2-oxidopyridinium: Syntheses, crystal structures and properties","authors":"","doi":"10.1016/j.ica.2024.122374","DOIUrl":"10.1016/j.ica.2024.122374","url":null,"abstract":"<div><p>In this work, we have synthesized six coordination polymers using the organic ligand 3-carboxy-1-(3′-carboxybenzyl)-2-oxidopyridinium (H<sub>2</sub>L). The compounds, named [Co(L)(H<sub>2</sub>O)<sub>2</sub>]<sub>n</sub> (<strong>1</strong>), [Co(L)(2,2′-bpy)(H<sub>2</sub>O)]<sub>n</sub> (<strong>2</strong>), [Co(L)(4,4′-bpy)<sub>0.5</sub>]<sub>n</sub> (<strong>3</strong>), [Mn<sub>2</sub>(L)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>n</sub> (<strong>4</strong>), [Mn(L)(2,2′-bpy)(H<sub>2</sub>O)]<sub>n</sub> (<strong>5</strong>) and [Mn(L)(phen)(H<sub>2</sub>O)]<sub>n</sub> (<strong>6</strong>), where 2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine and phen = 1,10-phenanthroline, were prepared under hydrothermal conditions and characterized using various physical measurements. The single-crystal X-ray diffraction analyses show that compounds <strong>1</strong>–<strong>6</strong> possess different structures because of multiple coordination modes and weak interactions. The Hirshfeld surface analyses of compounds <strong>1</strong>–<strong>6</strong> have also been studied in detail.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004651/pdfft?md5=32c913b42cd21f3793c5d1582e46752f&pid=1-s2.0-S0020169324004651-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142167748","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 : 2024-09-07DOI: 10.1016/j.ica.2024.122353
A novel N,N’-dimethylethylenediamine derivative of substituted bis(phenol)diamine ligands, namely 2-(tert-butyl)-4-methylphenol in H2L1, was synthesized by a convenient green procedure. Nickel)II) complex [NiL1] 1 has been synthesized and characterized by various methods along with crystal structure determined. Ni(II) coordination center in a mononuclear complex is surrounded by two phenolate oxygen atoms and two amine nitrogen atoms of the ligand in a square planar arrangement. The magnetic susceptibility of the title complex indicates a paramagnetic behavior above 150 K, while strong ferromagnetism below 100 K. Furthermore, the cyclic voltammetry studies show two ligand-centered oxidation of the phenolate groups to phenoxyl radical and the metal-centered reduction of Ni(II) to Ni(0). The Glaser coupling reaction of phenylacetylene was also studied. A strong catalytic activity at room T in THF solvent is observed for 1 in the presence of zinc powder as a reducing agent. A full conversion rate was achieved after 7 h at 25 °C. The DFT analysis corroborates with the square-planar NiO2N2 chromophore of 1 being reduced in catalytically active Ni(0) by applied Zn. The calculated Gibbs free energy of the reaction leading to the formation of the substrate Ni-complex is favorable endothermic. Most of the data for 1 were obtained also for the very similar previously reported [NiL2] 2, with 2,4- di tert-butylphenol in H2L2, which were than compared.
{"title":"Synthesis and characterization of catalytically active Ni(II) complexes with Bis(phenol)diamine ligands","authors":"","doi":"10.1016/j.ica.2024.122353","DOIUrl":"10.1016/j.ica.2024.122353","url":null,"abstract":"<div><p>A novel N,N’-dimethylethylenediamine derivative of substituted bis(phenol)diamine ligands, namely 2-(<em>tert-</em>butyl)-4-methylphenol in H<sub>2</sub>L<sup>1</sup>, was synthesized by a convenient green procedure. Nickel)II) complex [NiL<sup>1</sup>] <strong>1</strong> has been synthesized and characterized by various methods along with crystal structure determined. Ni(II) coordination center in a mononuclear complex is surrounded by two phenolate oxygen atoms and two amine nitrogen atoms of the ligand in a square planar arrangement. The magnetic susceptibility of the title complex indicates a paramagnetic behavior above 150 K, while strong ferromagnetism below 100 K. Furthermore, the cyclic voltammetry studies show two ligand-centered oxidation of the phenolate groups to phenoxyl radical and the metal-centered reduction of Ni(II) to Ni(0). The Glaser coupling reaction of phenylacetylene was also studied. A strong catalytic activity at room T in THF solvent is observed for <strong>1</strong> in the presence of zinc powder as a reducing agent. A full conversion rate was achieved after 7 h at 25 °C. The DFT analysis corroborates with the square-planar NiO<sub>2</sub>N<sub>2</sub> chromophore of <strong>1</strong> being reduced in catalytically active Ni(0) by applied Zn. The calculated Gibbs free energy of the reaction leading to the formation of the substrate Ni-complex is favorable endothermic. Most of the data for <strong>1</strong> were obtained also for the very similar previously reported [NiL<sup>2</sup>] <strong>2</strong>, with 2,4- di <em>tert-</em>butylphenol in H<sub>2</sub>L<sup>2</sup>, which were than compared.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004444/pdfft?md5=914e4167d534a4431b4cdeb3a6f7ab3f&pid=1-s2.0-S0020169324004444-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142167747","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 : 2024-09-06DOI: 10.1016/j.ica.2024.122368
Reactions of N‚N’-bis(3-methylpyridyl)oxalamide (L1), N‚N’-bis(3-methylpyridyl)adipoamide (L2) or N‚N’-bis(3-methylpyridyl)sebaamide (L3) with 1,2,4,5-benzenetetracarboxylic acid (1,2,4,5-H4BETC) and metal salt yield four coordination polymers: {[Cu2(L1)2(1,2,4,5-BTEC)(H2O)]·5H2O}n, 1, [Cu2(L2)(1,2,4,5-BTEC)(H2O)4]n, 2, [Cu2(L3)(1,2,4,5-BTEC)(H2O)4]n, 3, and [Ni(L2)(1,2,4,5-BTEC)0.5(H2O)2]n, 4. These polymers have been structurally characterized using single crystal X-ray crystallography. Complex 1 forms a 3D framework adopting a new (4.62)2(42.62.82)(42.64.84)2(63.83) topology, whereas the others display 2D layers with the bex topology for 2 and 3, and a rare 4,4L88 topology for 4. The structural diversity of these coordination polymers is influenced by the combined effects of metal identity and ligand flexibility, supported by the 1,2,4,5-BTEC4- ligand. Their thermal properties have also been investigated.
{"title":"Structural diversity in coordination polymers with benzenetetracarboxylate and bis-pyridyl-bis-amide","authors":"","doi":"10.1016/j.ica.2024.122368","DOIUrl":"10.1016/j.ica.2024.122368","url":null,"abstract":"<div><p>Reactions of <em>N</em>‚<em>N’</em>-bis(3-methylpyridyl)oxalamide (<strong>L<sup>1</sup></strong>), <em>N</em>‚<em>N’</em>-bis(3-methylpyridyl)adipoamide (<strong>L<sup>2</sup>)</strong> or <em>N</em>‚<em>N’</em>-bis(3-methylpyridyl)sebaamide (<strong>L<sup>3</sup></strong>) with 1,2,4,5-benzenetetracarboxylic acid (1,2,4,5-H<sub>4</sub>BETC) and metal salt yield four coordination polymers: {[Cu<sub>2</sub>(<strong>L<sup>1</sup></strong>)<sub>2</sub>(1,2,4,5-BTEC)(H<sub>2</sub>O)]·5H<sub>2</sub>O}<sub>n</sub>, <strong>1</strong>, [Cu<sub>2</sub>(<strong>L<sup>2</sup></strong>)(1,2,4,5-BTEC)(H<sub>2</sub>O)<sub>4</sub>]<sub>n</sub>, <strong>2</strong>, [Cu<sub>2</sub>(<strong>L<sup>3</sup></strong>)(1,2,4,5-BTEC)(H<sub>2</sub>O)<sub>4</sub>]<sub>n</sub>, <strong>3</strong>, and [Ni(<strong>L<sup>2</sup></strong>)(1,2,4,5-BTEC)<sub>0.5</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>n</sub>, <strong>4</strong>. These polymers have been structurally characterized using single crystal X-ray crystallography. Complex <strong>1</strong> forms a 3D framework adopting a new (4.6<sup>2</sup>)<sub>2</sub>(4<sup>2</sup>.6<sup>2</sup>.8<sup>2</sup>)(4<sup>2</sup>.6<sup>4</sup>.8<sup>4</sup>)<sub>2</sub>(6<sup>3</sup>.8<sup>3</sup>) topology, whereas the others display 2D layers with the <strong>bex</strong> topology for <strong>2</strong> and <strong>3</strong>, and a rare 4,4L88 topology for <strong>4</strong>. The structural diversity of these coordination polymers is influenced by the combined effects of metal identity and ligand flexibility, supported by the 1,2,4,5-BTEC<sup>4-</sup> ligand. Their thermal properties have also been investigated.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004596/pdfft?md5=8e061b0e0ad698f593a814cf5c3fdca8&pid=1-s2.0-S0020169324004596-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142162443","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 : 2024-09-06DOI: 10.1016/j.ica.2024.122369
Three Cu(II) complexes (CTS1-CTS3) of acenaphthene quinone thiosemicarbazone with various N-terminal substitutions were synthesized. The prepared compounds were characterized via different spectroscopic analyses. The square planar structure formed by the ligands with Cu(II) (tridentate manner, ONS donor) is confirmed through EPR spectral analysis. The DNA binding studies performed using UV–visible and fluorescence spectroscopy point out that, all complexes showing significant interaction with DNA and CTS2 were the strongest (Kb = 6.46 × 106 M−1 & Kapp = 2.5 × 106 M−1). A similar binding trend is observed towards the BSA protein (CTS2 with high Kb value, 1.76 × 105 M−1). The docking studies with EGFR protein (PDB ID: 5EDQ) reveal that CTS2 has the highest affinity towards them with a docking energy of − 7.41 Kcal/mol. The DFT investigations account for the stability (CTS3 has better structural stability with a high band gap, 0.10634 eV) and biological activity of complexes (CTS2 has a stronger biological activity due to its low ω value, 0.5864 eV). The lipophilicity (LogP ˃ 5) values obtained via Swiss-ADME studies are satisfactory and indicate that all 3 complexes have the potential to function as good oral drug candidates. The MTT assay results showed that CTS2 was the most effective against human breast (MCF-7), lung (A549), and cervical (HeLa) cancer cell lines, with IC50 values of 11.5, 43.9, and 19.6 μM, respectively. Conversely, CTS2 showed the least cytotoxicity (IC50 = 79.7 μM) when it came to normal (Vero) kidney epithelial cells.
{"title":"Synthesis and characterization of copper(II) complex derived from newly synthesized acenaphthene quinone thiosemicarbazone ligands: Computational studies, in vitro binding with DNA/BSA and anticancer studies","authors":"","doi":"10.1016/j.ica.2024.122369","DOIUrl":"10.1016/j.ica.2024.122369","url":null,"abstract":"<div><p>Three Cu(II) complexes (<strong>CTS1</strong>-<strong>CTS3</strong>) of acenaphthene quinone thiosemicarbazone with various <em>N</em>-terminal substitutions were synthesized. The prepared compounds were characterized via different spectroscopic analyses. The square planar structure formed by the ligands with Cu(II) (tridentate manner, ONS donor) is confirmed through EPR spectral analysis. The DNA binding studies performed using UV–visible and fluorescence spectroscopy point out that, all complexes showing significant interaction with DNA and <strong>CTS2</strong> were the strongest (K<sub>b</sub> = 6.46 × 10<sup>6</sup> M<sup>−1</sup> & K<sub>app</sub> = 2.5 × 10<sup>6</sup> M<sup>−1</sup>). A similar binding trend is observed towards the BSA protein (<strong>CTS2</strong> with high K<sub>b</sub> value, 1.76 × 10<sup>5</sup> M<sup>−1</sup>). The docking studies with EGFR protein (PDB ID: 5EDQ) reveal that <strong>CTS2</strong> has the highest affinity towards them with a docking energy of − 7.41 Kcal/mol. The DFT investigations account for the stability (<strong>CTS3</strong> has better structural stability with a high band gap, 0.10634 eV) and biological activity of complexes (<strong>CTS2</strong> has a stronger biological activity due to its low ω value, 0.5864 eV). The lipophilicity (LogP ˃ 5) values obtained via Swiss-ADME studies are satisfactory and indicate that all 3 complexes have the potential to function as good oral drug candidates. The MTT assay results showed that <strong>CTS2</strong> was the most effective against human breast (MCF-7), lung (A549), and cervical (HeLa) cancer cell lines, with IC<sub>50</sub> values of 11.5, 43.9, and 19.6 μM, respectively. Conversely, <strong>CTS2</strong> showed the least cytotoxicity (IC<sub>50</sub> = 79.7 μM) when it came to normal (Vero) kidney epithelial cells.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004602/pdfft?md5=2beeb0456441305529344f62172b2756&pid=1-s2.0-S0020169324004602-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142162444","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 : 2024-09-05DOI: 10.1016/j.ica.2024.122356
The series of titanium (IV) complexes trans-[TiCl4(OPPh3)2] (1), trans-[TiBr4(OPPh3)2] (2) and trans-[TiI4(OPPh3)2] (3) were obtained as polycrystalline powders by heating the corresponding metal tetrahalides with triphenylphosphine oxide in evacuated sealed glass ampoules. The crystal structures were determined by single crystal X-ray diffraction. Compounds 1 and 2 were isolated as yellow and brown crystalline powders, with yields 70 and 75%, respectively. This paper discusses the synthesis of these coordination compounds 1–3 and their crystal structures, and analyzes the geometric parameters of the related molecular complexes of niobium and rhenium for use in the design of magnetically diluted systems.
{"title":"The synthesis and crystal structure of the molecular complexes trans-[TiIVX4(OPPh3)2] (X = Cl, Br, I)","authors":"","doi":"10.1016/j.ica.2024.122356","DOIUrl":"10.1016/j.ica.2024.122356","url":null,"abstract":"<div><p>The series of titanium (IV) complexes <em>trans</em>-[TiCl<sub>4</sub>(OPPh<sub>3</sub>)<sub>2</sub>] (<strong>1</strong>), <em>trans</em>-[TiBr<sub>4</sub>(OPPh<sub>3</sub>)<sub>2</sub>] (<strong>2</strong>) and <em>trans</em>-[TiI<sub>4</sub>(OPPh<sub>3</sub>)<sub>2</sub>] (<strong>3</strong>) were obtained as polycrystalline powders by heating the corresponding metal tetrahalides with triphenylphosphine oxide in evacuated sealed glass ampoules. The crystal structures were determined by single crystal X-ray diffraction. Compounds <strong>1</strong> and <strong>2</strong> were isolated as yellow and brown crystalline powders, with yields 70 and 75%, respectively. This paper discusses the synthesis of these coordination compounds <strong>1</strong>–<strong>3</strong> and their crystal structures, and analyzes the geometric parameters of the related molecular complexes of niobium and rhenium for use in the design of magnetically diluted systems.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S002016932400447X/pdfft?md5=1ee9d1fd27e0173b03bc82be4d6adee8&pid=1-s2.0-S002016932400447X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142157883","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 : 2024-09-05DOI: 10.1016/j.ica.2024.122363
In this paper, the coordination of 4-methylpyrazole (L) to Ni(II) and Zn(II) ions is studied through the reactions of Ni(OAc)2·4H2O and Zn(OAc)2·2H₂O with 4-methylpyrazole in a 1:2 metal-to-ligand molar ratio in ethanol at room temperature. From the reaction mixtures, new complex compounds of formulae: [Ni(OAc)2L4] and [Zn(OAc)2L2] were crystallized. The crystal and molecular structure of the synthesized complexes were determined by single-crystal X-ray structure analysis. The coordination environment of Ni(II) in its complex is octahedral, while that of Zn(II) is tetrahedral. The compounds are characterized by IR spectra and elemental analysis. Their thermal stability, a crucial property, is analyzed by thermogravimetry. To get a better insight into the decomposition mechanism coupled TG-MS measurements were carried out, too. The tests of the antioxidative activity of the new complexes on DPPH radical showed that the Zn(II) complex is more effective than the Ni(II) complex.
{"title":"Synthesis, characterization and antioxidative capacity of nickel(II) and zinc(II) complexes with 4-methylpyrazole","authors":"","doi":"10.1016/j.ica.2024.122363","DOIUrl":"10.1016/j.ica.2024.122363","url":null,"abstract":"<div><p>In this paper, the coordination of 4-methylpyrazole (L) to Ni(II) and Zn(II) ions is studied through the reactions of Ni(OAc)<sub>2</sub>·4H<sub>2</sub>O and Zn(OAc)<sub>2</sub>·2H₂O with 4-methylpyrazole in a 1:2 metal-to-ligand molar ratio in ethanol at room temperature. From the reaction mixtures, new complex compounds of formulae: [Ni(OAc)<sub>2</sub>L<sub>4</sub>] and [Zn(OAc)<sub>2</sub>L<sub>2</sub>] were crystallized. The crystal and molecular structure of the synthesized complexes were determined by single-crystal X-ray structure analysis. The coordination environment of Ni(II) in its complex is octahedral, while that of Zn(II) is tetrahedral. The compounds are characterized by IR spectra and elemental analysis. Their thermal stability, a crucial property, is analyzed by thermogravimetry. To get a better insight into the decomposition mechanism coupled TG-MS measurements were carried out, too. The tests of the antioxidative activity of the new complexes on DPPH radical showed that the Zn(II) complex is more effective than the Ni(II) complex.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004547/pdfft?md5=c6f05fd8d6485d78fe59ae4e552aaf43&pid=1-s2.0-S0020169324004547-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142149495","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 : 2024-09-05DOI: 10.1016/j.ica.2024.122367
Halochromism has a plethora of uses in the textile industry, including wound treatments and protective apparel. Reactive dye’s fastness and a wide variety of hues, from bright to dull, make it ideal for coloring cotton and other regenerated cellulose fibers. It is also fundamentally paramount importance to determine the freshness of packaging foods. In this study, a halochromic probe, 4,4′-((1E,1′E,3E,3′E)-hydrazine-1,2-diylidenebis(prop-1-en-1-yl-3-ylidene))bis(N, N-dimethylaniline), HDBD, has been introduced utilizing a simple condensation reaction. Through the protonation and deprotonation process with the addition of acid and base in the non-aqueous medium, HDBD shows visual colorimetric as well as ratiometric UV–visible absorption spectral change. A colorimetric paper strip-based experiment has been demonstrated to detect trace amounts of acid and its reversibility with bases in non-aqueous solvents. Further, a dip-stick experiment was also carried out for the detection of acid-base vapor in a wide range of concentrations. Furthermore, the overlapping indicator method is explored to estimate acid dissociation constants in the non-aqueous medium. Moreover, we have constructed the INHIBIT (INH) and IMPLICATION (IMP) molecular logic gates exploring the reversibility of HDBD due to the cascade introduction of acid-base as chemical encoded inputs. Utilizing a reversible and reproducible detecting method, we have constructed a molecular-scale additional memory device that demonstrates binary logic “Writing-Reading-Erasing-Reading” and “Multi-write” functions. This finding provides a new way for designing acid-base indicators, which could estimate the acid dissociation constants of various acids in the non-aqueous environment which is fundamentally important in the field of acid-catalyzed organic synthesis.
{"title":"An azine‐based halochromic molecular chameleon","authors":"","doi":"10.1016/j.ica.2024.122367","DOIUrl":"10.1016/j.ica.2024.122367","url":null,"abstract":"<div><p>Halochromism has a plethora of uses in the textile industry, including wound treatments and protective apparel. Reactive dye’s fastness and a wide variety of hues, from bright to dull, make it ideal for coloring cotton and other regenerated cellulose fibers. It is also fundamentally paramount importance to determine the freshness of packaging foods. In this study, a halochromic probe, 4,4′-((1E,1′E,3E,3′E)-hydrazine-1,2-diylidenebis(prop-1-en-1-yl-3-ylidene))bis(N, <em>N</em>-dimethylaniline), <strong>HDBD</strong>, has been introduced utilizing a simple condensation reaction. Through the protonation and deprotonation process with the addition of acid and base in the non-aqueous medium, <strong>HDBD</strong> shows visual colorimetric as well as ratiometric UV–visible absorption spectral change. A colorimetric paper strip-based experiment has been demonstrated to detect trace amounts of acid and its reversibility with bases in non-aqueous solvents. Further, a dip-stick experiment was also carried out for the detection of acid-base vapor in a wide range of concentrations. Furthermore, the overlapping indicator method is explored to estimate acid dissociation constants in the non-aqueous medium. Moreover, we have constructed the <strong>INHIBIT</strong> (INH) and <strong>IMPLICATION</strong> (IMP) molecular logic gates exploring the reversibility of <strong>HDBD</strong> due to the cascade introduction of acid-base as chemical encoded inputs. Utilizing a reversible and reproducible detecting method, we have constructed a molecular-scale additional memory device that demonstrates binary logic “Writing-Reading-Erasing-Reading” and “Multi-write” functions. This finding provides a new way for designing acid-base indicators, which could estimate the acid dissociation constants of various acids in the non-aqueous environment which is fundamentally important in the field of acid-catalyzed organic synthesis.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004584/pdfft?md5=d1c425f432e03877931f698363f76915&pid=1-s2.0-S0020169324004584-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142162370","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 : 2024-09-04DOI: 10.1016/j.ica.2024.122349
The geometrical and stability properties of Ru-doped silver clusters (AgnRu with n = 1–13) are investigated by density functional theory (DFT) calculations. The results show that the Ru dopant adopts central positions in the lowest-energy structures of AgnRu clusters. The most stable structures found are planar and curved for n = 3–6, while for n = 6 onward the structures follow a pentagonal growth pattern. Interestingly for n = 10, we found a cage structure with fulfills the 18 electron rule. The relative stability of the clusters is further evaluated through energetic parameters such as ionization energy, electron affinity, second order energy difference and HOMO–LUMO gap. The results show that the most stable structures in this series are Ag3Ru, Ag6Ru and Ag10Ru, as supported by electronic structure analyses. The plausible formation of the Ag10Ru cluster as a superatomic species is rationalized with 1.64 eV of HOMO–LUMO gap and 6.23 eV of adiabatic ionization energy.
通过密度泛函理论(DFT)计算研究了掺杂 Ru 的银簇(AgnRu,n = 1-13)的几何和稳定性能。结果表明,掺杂的 Ru 在 AgnRu 团簇的最低能结构中占据中心位置。对于 n = 3-6,最稳定的结构是平面和曲线结构,而对于 n = 6 以上,结构则遵循五边形生长模式。有趣的是,当 n = 10 时,我们发现了一种符合 18 电子规则的笼状结构。通过电离能、电子亲和力、二阶能差和 HOMO-LUMO 间隙等能量参数,我们进一步评估了这些团簇的相对稳定性。结果表明,该系列中最稳定的结构是 Ag3Ru、Ag6Ru 和 Ag10Ru,电子结构分析也证明了这一点。根据 1.64 eV 的 HOMO-LUMO 间隙和 6.23 eV 的绝热电离能,Ag10Ru 团簇作为超原子物种的形成是合理的。
{"title":"Structures and stabilities Ru-doped Agn (n = 1–13) clusters: Ag10Ru a 18-ve cluster superatom","authors":"","doi":"10.1016/j.ica.2024.122349","DOIUrl":"10.1016/j.ica.2024.122349","url":null,"abstract":"<div><p>The geometrical and stability properties of Ru-doped silver clusters (Ag<sub>n</sub>Ru with n = 1–13) are investigated by density functional theory (DFT) calculations. The results show that the Ru dopant adopts central positions in the lowest-energy structures of Ag<sub>n</sub>Ru clusters. The most stable structures found are planar and curved for n = 3–6, while for n = 6 onward the structures follow a pentagonal growth pattern. Interestingly for n = 10, we found a cage structure with fulfills the 18 electron rule. The relative stability of the clusters is further evaluated through energetic parameters such as ionization energy, electron affinity, second order energy difference and HOMO–LUMO gap. The results show that the most stable structures in this series are Ag<sub>3</sub>Ru, Ag<sub>6</sub>Ru and Ag<sub>10</sub>Ru, as supported by electronic structure analyses. The plausible formation of the Ag<sub>10</sub>Ru cluster as a superatomic species is rationalized with 1.64 eV of HOMO–LUMO gap and 6.23 eV of adiabatic ionization energy.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004407/pdfft?md5=05b5f43922c230198cbeb05349785a06&pid=1-s2.0-S0020169324004407-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142162442","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}