Pub Date : 2024-08-23DOI: 10.1016/j.ica.2024.122342
A 6-(thiophen-2-yl)benzo[4,5]thieno[3,2-c]quinoline (QTP), with thiophene and quinoline based moieties as binding sites, has been synthesized and characterized with spectroscopic methods, and DFT. The synthesized probe QTP showed highly sensitive and highly specific fluorescent ‘turn-on’ effect (λem = 280 nm) for the 1:1 binding with Fe3+ ions to form probe QTP.Fe3+ complex in semi-aqueous medium (acetonitrile:water (50:50; v/v)) and live cells. The 1:1 binding stoichiometry of probe QTP and Fe3+ ions were proposed by DFT calculations and confirmed by the NMR spectroscopy, and mass spectrum of probe QTP.Fe3+ complex. Importantly, with the LOD 6.37 µM for the detection of Fe3+ ions, receptor QTP did not show any interference from potentially competing ions, indicates its biocompatibility. The micromolar limit of detection (6.37 µM), cell permeability, and low cytotoxicity allows the probe QTP to be an outstanding tool for the live-cell imaging and detection of ferric ions in live cells.
{"title":"Benzothieno[c]quinoline based a novel fluorescent “turn-on” chemosensor for the detection of Fe (III) from aqueous solution","authors":"","doi":"10.1016/j.ica.2024.122342","DOIUrl":"10.1016/j.ica.2024.122342","url":null,"abstract":"<div><p>A 6-(thiophen-2-yl)benzo[4,5]thieno[3,2-<em>c</em>]quinoline (QTP), with thiophene and quinoline based moieties as binding sites, has been synthesized and characterized with spectroscopic methods, and DFT. The synthesized probe QTP showed highly sensitive and highly specific fluorescent ‘turn-on’ effect (λem = 280 nm) for the 1:1 binding with Fe<sup>3+</sup> ions to form probe QTP.Fe<sup>3+</sup> complex in semi-aqueous medium (acetonitrile:water (50:50; v/v)) and live cells. The 1:1 binding stoichiometry of probe QTP and Fe<sup>3+</sup> ions were proposed by DFT calculations and confirmed by the NMR spectroscopy, and mass spectrum of probe QTP.Fe<sup>3+</sup> complex. Importantly, with the LOD 6.37 µM for the detection of Fe<sup>3+</sup> ions, receptor QTP did not show any interference from potentially competing ions, indicates its biocompatibility. The micromolar limit of detection (6.37 µM), cell permeability, and low cytotoxicity allows the probe QTP to be an outstanding tool for the live-cell imaging and detection of ferric ions in live cells.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142099332","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 : 2024-08-22DOI: 10.1016/j.ica.2024.122325
The reaction of monooxidized thioyl (4-CH3)C6H3N-2-NH(P(S)Ph2) (1) ligand with MCl2(COD)(M = Pd, Pt) in equimolar ratio resulted in cis-[MCl2{1-κ2S,Npy}] (M = Pd (2), Pt(3)) complexes. Also, The reaction of 1 with HgX2 (X = Cl, I) produced cis-[HgX2{1-κ2S,Npy }] (X = Cl(4), I(5)). Complexes 2–5 have been isolated and characterized by multinuclear NMR (1H, 13C, and 31P) and IR spectroscopy. The molecular structures of 2, 4, and 5 were determined using single X-ray crystallography. 4 and 5 are the first structurally defined instances of this type of κ2S,Npy -bidentate ligand with Hg(II) metal complexes. The new palladium(II) complex 2 as a pre-catalyst in the Suzuki cross-coupling process was also investigated.
{"title":"Pd(II), Pt(II), and novel Hg(II) metal complexes of N-(diphenylphosphinothioyl)-2-(4-methylpyridyl) amine chelating ligand: Synthesis, characterization, X-ray structures and catalytic activity of Pd(II) derivative in the Suzuki cross-coupling reaction","authors":"","doi":"10.1016/j.ica.2024.122325","DOIUrl":"10.1016/j.ica.2024.122325","url":null,"abstract":"<div><p>The reaction of monooxidized thioyl (4-CH<sub>3</sub>)C<sub>6</sub>H<sub>3</sub>N-2-NH(P(S)Ph<sub>2</sub>) (<strong>1</strong>) ligand with MCl<sub>2</sub>(COD)(M = Pd, Pt) in equimolar ratio resulted in <em>cis</em>-[MCl<sub>2</sub>{<strong>1</strong>-κ<sup>2</sup><em>S,N<sup>py</sup></em>}] (M = Pd (<strong>2</strong>), Pt(<strong>3</strong>)) complexes. Also, The reaction of <strong>1</strong> with HgX<sub>2</sub> (X = Cl, I) produced <em>cis</em>-[HgX<sub>2</sub>{<strong>1</strong>-κ<sup>2</sup><em>S,N<sup>py</sup></em> }] (X = Cl(<strong>4</strong>), I(<strong>5</strong>)). Complexes <strong>2</strong>–<strong>5</strong> have been isolated and characterized by multinuclear NMR (<sup>1</sup>H, <sup>13</sup>C, and <sup>31</sup>P) and IR spectroscopy. The molecular structures of <strong>2</strong>, <strong>4</strong>, and <strong>5</strong> were determined using single X-ray crystallography. <strong>4</strong> and <strong>5</strong> are the first structurally defined instances of this type of κ<sup>2</sup><em>S,N<sup>py</sup></em> -bidentate ligand with Hg(II) metal complexes. The new palladium(II) complex <strong>2</strong> as a pre-catalyst in the Suzuki cross-coupling process was also investigated.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142049088","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 : 2024-08-22DOI: 10.1016/j.ica.2024.122323
A copper(II)/potassium(I) Schiff base polymeric complex has been synthesized and characterized. Salen-type N2O2O2′ donor compartmental Schiff base ligand has been used where copper(II) resides in the inner N2O2 core and potassium (I) sits in the outer O2O2′ core. Single crystal X-ray analysis revealed that the unintended formation of a disordered bromine atom led to Cu⋯Br π-hole coinage bond (CiB) interaction. The energetics regarding the CiB interactions have been rationalized using DFT calculations, QTAIM, and ELF study.
{"title":"An experimental and theoretical study of coinage bond interaction in a copper(II)/potassium(I) Schiff base complex","authors":"","doi":"10.1016/j.ica.2024.122323","DOIUrl":"10.1016/j.ica.2024.122323","url":null,"abstract":"<div><p>A copper(II)/potassium(I) Schiff base polymeric complex has been synthesized and characterized. Salen-type N<sub>2</sub>O<sub>2</sub>O<sub>2</sub>′ donor compartmental Schiff base ligand has been used where copper(II) resides in the inner N<sub>2</sub>O<sub>2</sub> core and potassium (I) sits in the outer O<sub>2</sub>O<sub>2</sub>′ core. Single crystal X-ray analysis revealed that the unintended formation of a disordered bromine atom led to Cu⋯Br π-hole coinage bond (CiB) interaction. The energetics regarding the CiB interactions have been rationalized using DFT calculations, QTAIM, and ELF study.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142099334","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 : 2024-08-22DOI: 10.1016/j.ica.2024.122322
Herein, a homobimetallic azomethine-functionalized nickel(II) complex, [Ni2L2(van)(μ1,1-NCS)] (AMR-1, where L = 2-[(2-Hydroxy-1,1-dimethyl-ethylimino)-methyl]-6-methoxyphenol, molecular weight = 788.20 (found)) has been judiciously synthesized with N-coordinated end-on thiocyanate. AMR-1 exhibited promising chromogenic variation from pale green to colourless with hypochromic shifting in the visible region in the presence of silver(I). Herein, the exposed sulfur site of the co-ligand acts as chemodosimetric recognition site for highly selective detection of a soft metal pollutant, silver ion (Ag+) with the limit of detection (LOD) of 0.37 ppm. Along with this, aqueous cyanide (CN−) recognition was accomplished in a mutually independent way with distinct chromogenic variation from pale green to yellowish color within ∼5 s. This led to the LOD of 0.46 ppm, which is much lower than the safe limit, set by the World Health Organization (WHO). The stability constant value for cyanide interaction with AMR-1 is obtained to be 1.49 × 103 M−1 as per 1:1 binding stoichiometry. Experimental findings, obtained from UV–Vis, HR-MS, FT-IR, and 1H NMR spectroscopic studies in conjugation with the decreased HOMO-LUMO energy gap from 3.40 eV to 2.07 eV, obtained from density functional theory studies, support the mechanistic pathway of interaction. Implementing molecular logic platforms benefits from fabricating three-input-two-output logic circuits by imitating variable spectroscopic outcomes. Real-time multifarious applications of AMR-1 have been accomplished with paper strip-based solid-state assay and recognition of the target-specific analytes from targeted medicinal specimens and from both cyanogenic as well as non-cyanogenic food sources. To the best of our knowledge, this is probably the first nickel(II) complex derived sensory receptor that is effectually implemented towards recognition of another metal ion, silver (I) along with CN− from aqueous as well as from real specimens.
在此,我们用硫氰酸 N 配位末端来合成了一种偶氮金属功能化镍(II)配合物 [Ni2L2(van)(μ1,1-NCS)](AMR-1,其中 L = 2-[(2-羟基-1,1-二甲基-乙基亚氨基)-甲基]-6-甲氧基苯酚,分子量 = 788.20(已发现))。在银(I)的存在下,AMR-1 表现出从淡绿色到无色的良好色度变化,并在可见光区域出现低色度偏移。在这里,共配体暴露的硫位点可作为化学计量识别位点,对软金属污染物银离子(Ag+)进行高选择性检测,检测限(LOD)为 0.37 ppm。与此同时,水体中的氰化物(CN-)也能以相互独立的方式被识别,并在 5 秒内从淡绿色变为淡黄色。根据 1:1 的结合化学计量学,氰化物与 AMR-1 作用的稳定常数为 1.49 × 103 M-1。紫外可见光谱、HR-MS、傅立叶变换红外光谱和 1H NMR 光谱研究得出的共轭实验结果,以及密度泛函理论研究得出的 HOMO-LUMO 能隙从 3.40 eV 减小到 2.07 eV 的结果,支持了相互作用的机理途径。分子逻辑平台的实现得益于通过模仿可变光谱结果来制造三输入两输出逻辑电路。AMR-1 的实时多种应用已通过基于纸条的固态检测实现,并可从目标药物标本和含氰及不含氰的食物来源中识别目标特异性分析物。据我们所知,这可能是第一个由镍(II)络合物衍生的感官受体,可有效识别水体和实际样本中的另一种金属离子银(I)和氯化萘。
{"title":"A homobimetallic nickel(II) complex for discriminative chromogenic recognition of aqueous cyanide and silver(I) from medicinal products: Role of end-on thiocyanate bridging","authors":"","doi":"10.1016/j.ica.2024.122322","DOIUrl":"10.1016/j.ica.2024.122322","url":null,"abstract":"<div><p>Herein, a homobimetallic azomethine-functionalized nickel(II) complex, [Ni<sub>2</sub>L<sub>2</sub>(van)(μ<sub>1,1</sub>-NCS)] (<strong>AMR-1</strong>, where L = 2-[(2-Hydroxy-1,1-dimethyl-ethylimino)-methyl]-6-methoxyphenol, molecular weight = 788.20 (found)) has been judiciously synthesized with <em>N</em>-coordinated end-on thiocyanate. <strong>AMR-1</strong> exhibited promising chromogenic variation from pale green to colourless with hypochromic shifting in the visible region in the presence of silver(I). Herein, the exposed sulfur site of the co-ligand acts as chemodosimetric recognition site for highly selective detection of a soft metal pollutant, silver ion (Ag<sup>+</sup>) with the limit of detection (LOD) of 0.37 ppm. Along with this, aqueous cyanide (CN<sup>−</sup>) recognition was accomplished in a mutually independent way with distinct chromogenic variation from pale green to yellowish color within ∼5 s. This led to the LOD of 0.46 ppm, which is much lower than the safe limit, set by the World Health Organization (WHO). The stability constant value for cyanide interaction with <strong>AMR-1</strong> is obtained to be 1.49 × 10<sup>3</sup> M<sup>−1</sup> as per 1:1 binding stoichiometry. Experimental findings, obtained from UV–Vis, HR-MS, FT-IR, and <sup>1</sup>H NMR spectroscopic studies in conjugation with the decreased HOMO-LUMO energy gap from 3.40 eV to 2.07 eV, obtained from density functional theory studies, support the mechanistic pathway of interaction. Implementing molecular logic platforms benefits from fabricating <em>three-input-two-output</em> logic circuits by imitating variable spectroscopic outcomes. Real-time multifarious applications of <strong>AMR-1</strong> have been accomplished with paper strip-based solid-state assay and recognition of the target-specific analytes from targeted medicinal specimens and from both cyanogenic as well as non-cyanogenic food sources. To the best of our knowledge, this is probably the first nickel(II) complex derived sensory receptor that is effectually implemented towards recognition of another metal ion, silver (I) along with CN<sup>−</sup> from aqueous as well as from real specimens.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142048041","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 : 2024-08-21DOI: 10.1016/j.ica.2024.122326
Two new 2D Mn(II)-based coordination polymers (CPs), {[Mn(H3L)(phen)]·H2O}n (1) and {[Mn(H3L)(bpy)]·1.5H2O}n (2), were synthesized using one pot procedure. They were isolated from 2,4-bis(3,5-dicarboxylphenxoy)benzoic acid (H5L) and two chelating N-donor ligands 1,10-Phenanthroline (phen) and 2,2′-bipyridine (bpy) for photocatalytic applications. The identification of the complexes was confirmed through elemental analysis, FTIR, PXRD, crystallography, and TG analysis, confirming distorted octahedral NNO4 coordination of Mn(II) with the carboxylate O atoms chelating and syn-syn bridging mode (1) and (2). Powder XRD confirmed phase-purity, while TG analysis indicated thermal stability of the complexes up to 400 °C. Both Mn(II)-based coordination polymers (1) and (2) showed optical semiconducting behavior, making them suitable candidates for photocatalysis. The Mn(II)-based coordination polymers (1) showed a 91.93 % degradation of nitrofurazone (NFZ) through photodecomposition. The trapping experiment established that the catalysis of NFZ photodecomposition is primarily attributed to O2− radicals.
{"title":"Two new Mn(II)-based coordination polymers built by multicarboxylate for photocatalytic elimination of nitrofurazone","authors":"","doi":"10.1016/j.ica.2024.122326","DOIUrl":"10.1016/j.ica.2024.122326","url":null,"abstract":"<div><p>Two new 2D Mn(II)-based coordination polymers (CPs), {[Mn(H<sub>3</sub>L)(phen)]·H<sub>2</sub>O}<sub>n</sub> (<strong>1</strong>) and {[Mn(H<sub>3</sub>L)(bpy)]·1.5H<sub>2</sub>O}<sub>n</sub> (<strong>2</strong>), were synthesized using one pot procedure. They were isolated from 2,4-bis(3,5-dicarboxylphenxoy)benzoic acid (H<sub>5</sub>L) and two chelating <em>N</em>-donor ligands 1,10-Phenanthroline (phen) and 2,2′-bipyridine (bpy) for photocatalytic applications. The identification of the complexes was confirmed through elemental analysis, FTIR, PXRD, crystallography, and TG analysis, confirming distorted octahedral N<img>N<img>O4 coordination of Mn(II) with the carboxylate O atoms chelating and <em>syn</em>-<em>syn</em> bridging mode (<strong>1</strong>) and (<strong>2</strong>). Powder XRD confirmed phase-purity, while TG analysis indicated thermal stability of the complexes up to 400 °C. Both Mn(II)-based coordination polymers (<strong>1</strong>) and (<strong>2</strong>) showed optical semiconducting behavior, making them suitable candidates for photocatalysis. The Mn(II)-based coordination polymers (<strong>1</strong>) showed a 91.93 % degradation of nitrofurazone (NFZ) through photodecomposition. The trapping experiment established that the catalysis of NFZ photodecomposition is primarily attributed to O<sub>2</sub><sup><img>−</sup> radicals.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142089303","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 : 2024-08-21DOI: 10.1016/j.ica.2024.122321
Metal ions participate in numerous essential biological processes in our body. In the external environment, metal ions are present in food, soil, and water. However, the presence of metal ions concentration above the permissible limits may cause hazardous effect on environment and human beings. Therefore, detection of metal ions with high selectivity and sensitivity is important for biological system and in environmental monitoring. In literature, several examples employing Schiff base derivatives or MNPs as optical sensors for metal ions were investigated. However, studies on the development of Schiff base stabilized metal nanoparticles as optical sensors for hazardous metal ions are scanty in the literature. At present, it is essential to be able to construct controlled ultra-small, highly dispersed, stable, and functionalized metal nanoparticles (MNPs) to make them suitable for industrial applications. The production of Schiff base stabilized metal nanoparticles (MNPs) can be achieved easily without demanding experimental requirements. As a result, it provides a simple, quick, and effective approach to create highly efficient catalysts for the treatment of environmental pollutants. Herein, we report Schiff base and organic ligand stabilized metal nanoparticles as potential chemosensors for hazardous metal ions.
{"title":"Schiff base and organic ligand stabilized metal nanoparticles as potential chemosensors for hazardous metal ions: Design, principle, optical signaling mechanism and application","authors":"","doi":"10.1016/j.ica.2024.122321","DOIUrl":"10.1016/j.ica.2024.122321","url":null,"abstract":"<div><p>Metal ions participate in numerous essential biological processes in our body. In the external environment, metal ions are present in food, soil, and water. However, the presence of metal ions concentration above the permissible limits may cause hazardous effect on environment and human beings. Therefore, detection of metal ions with high selectivity and sensitivity is important for biological system and in environmental monitoring. In literature, several examples employing Schiff base derivatives or MNPs as optical sensors for metal ions were investigated. However, studies on the development of Schiff base stabilized metal nanoparticles as optical sensors for hazardous metal ions are scanty in the literature. At present, it is essential to be able to construct controlled ultra-small, highly dispersed, stable, and functionalized metal nanoparticles (MNPs) to make them suitable for industrial applications. The production of Schiff base stabilized metal nanoparticles (MNPs) can be achieved easily without demanding experimental requirements. As a result, it provides a simple, quick, and effective approach to create highly efficient catalysts for the treatment of environmental pollutants. Herein, we report Schiff base and organic ligand stabilized metal nanoparticles as potential chemosensors for hazardous metal ions.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142049087","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 : 2024-08-20DOI: 10.1016/j.ica.2024.122320
Three transition metal complexes of s-triazine ligand (MorphBPT) were synthesized, characterized, and their supramolecular structures are explored. Their structures are confirmed to be [Co(MorphBPT)2](ClO4)2 (1), [Mn(MorphBPT)2](ClO4)2 (2), and [Ni(MorphBPT)(H2O)3]Cl2·2H2O (3) using single crystal X-ray diffraction. In all cases, the MorphBPT is a tridentate N-chelator. Hence, the metal ions have hexa-coordination environment in all complexes. In the two homoleptic complexes 1 and 2, the O···H, C···H, and C···O contacts, in addition to some short N···O and H···H contacts detected only in 2, are the most important. For 3, the Cl···H, O···H, and C···H contacts are the most significant. Enrichment ratio was used to detect the atom pairs which have the highest probability to form non-covalent interactions. The nature of MN and MO coordination interactions is analyzed with the aid of AIM calculations. Also, the interactions with the ligand moieties lowers the charge of Co(II), Ni(II), and Mn(II) to 0.8411, 0.9332, and 0.8308 e, respectively. The three complexes 1, 2, and 3 exhibited antibacterial activity exceeds the reference drug gentamicin against P. vulgaris where the diameter of the inhibition zones (DIZs) are determined to be 28, 29, 27, and 25 mm, respectively. In addition, 1 and 2 have antifungal activity better (DIZ = 18 mm) and equal (DIZ = 17 mm) compared to ketoconazole against A. fumigatus, respectively. The Mn(II) complex 2 is the most active against MCF-7 (75.3 ± 3.1 μM) and A-549 (40.2 ± 2.7 μM) cancerous cell lines.
{"title":"Synthesis of Co(II), Mn(II), and Ni(II) complexes with 4-(4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)morpholine; X-ray structure, Hirshfeld, AIM, and biological studies","authors":"","doi":"10.1016/j.ica.2024.122320","DOIUrl":"10.1016/j.ica.2024.122320","url":null,"abstract":"<div><p>Three transition metal complexes of <em>s</em>-triazine ligand (<strong><sup>Morph</sup>BPT</strong>) were synthesized, characterized, and their supramolecular structures are explored. Their structures are confirmed to be [Co(<sup>Morph</sup>BPT)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> (<strong>1</strong>), [Mn(<sup>Morph</sup>BPT)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> (<strong>2</strong>), and [Ni(<sup>Morph</sup>BPT)(H<sub>2</sub>O)<sub>3</sub>]Cl<sub>2</sub>·2H<sub>2</sub>O (<strong>3</strong>) using single crystal X-ray diffraction. In all cases, the <strong><sup>Morph</sup>BPT</strong> is a tridentate <em>N</em>-chelator. Hence, the metal ions have hexa-coordination environment in all complexes. In the two homoleptic complexes <strong>1</strong> and <strong>2</strong>, the O···H, C···H, and C···O contacts, in addition to some short N···O and H···H contacts detected only in <strong>2</strong>, are the most important. For <strong>3</strong>, the Cl···H, O···H, and C···H contacts are the most significant. Enrichment ratio was used to detect the atom pairs which have the highest probability to form non-covalent interactions. The nature of M<img>N and M<img>O coordination interactions is analyzed with the aid of AIM calculations. Also, the interactions with the ligand moieties lowers the charge of Co(II), Ni(II), and Mn(II) to 0.8411, 0.9332, and 0.8308 e, respectively. The three complexes <strong>1</strong>, <strong>2</strong>, and <strong>3</strong> exhibited antibacterial activity exceeds the reference drug gentamicin against <em>P. vulgaris</em> where the diameter of the inhibition zones (DIZs) are determined to be 28, 29, 27, and 25 mm, respectively. In addition, <strong>1</strong> and <strong>2</strong> have antifungal activity better (DIZ = 18 mm) and equal (DIZ = 17 mm) compared to ketoconazole against <em>A. fumigatus</em>, respectively. The Mn(II) complex <strong>2</strong> is the most active against MCF-7 (75.3 ± 3.1 μM) and A-549 (40.2 ± 2.7 μM) cancerous cell lines.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142040199","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 : 2024-08-18DOI: 10.1016/j.ica.2024.122324
In the past decades, lanthanide(III) complexes from the Schiff base ligands have received attention for their marvelous luminescence properties. Accordingly, their complexes have been used in a variety of applications in optical, biological and environmental fields. In this review, the structural and sensitization aspects of the lanthanide(III) Schiff base complexes have been investigated. The factors that induce their luminescence properties through efficient energy transfer pathways have been discussed thoroughly, such as (1) metal’s geometry, (2) ligand’s design and the preferred binding modes, (3) temperature and (4) molecular aggregation. In addition, the nature of the low-lying excited triplet state initiated from (1) intra-ligand charge transfer, ILCT, (2) ligand to metal charge transfer, LMCT, (3) ligand–ligand interaction, LLI, or (4) mixed d-f or f-f excited states in a single molecule, have also been discussed in detail.
{"title":"Factors that influence the energy transfer pathways in luminescent lanthanide Schiff base complexes","authors":"","doi":"10.1016/j.ica.2024.122324","DOIUrl":"10.1016/j.ica.2024.122324","url":null,"abstract":"<div><p>In the past decades, lanthanide(III) complexes from the Schiff base ligands have received attention for their marvelous luminescence properties. Accordingly, their complexes have been used in a variety of applications in optical, biological and environmental fields. In this review, the structural and sensitization aspects of the lanthanide(III) Schiff base complexes have been investigated. The factors that induce their luminescence properties through efficient energy transfer pathways have been discussed thoroughly, such as (1) metal’s geometry, (2) ligand’s design and the preferred binding modes, (3) temperature and (4) molecular aggregation. In addition, the nature of the low-lying excited triplet state initiated from (1) intra-ligand charge transfer, ILCT, (2) ligand to metal charge transfer, LMCT, (3) ligand–ligand interaction, LLI, or (4) mixed <em>d</em>-<em>f</em> or <em>f-f</em> excited states in a single molecule, have also been discussed in detail.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142006341","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 : 2024-08-14DOI: 10.1016/j.ica.2024.122314
The scaffold tris(8-quinolinyl)phosphite, (P(Oquin)3), can bind to metal centers as a bi- or a tridentate tripodal ligand, depending on the synthetic conditions and characteristics of the metal atom. Here the study of the coordinating properties of such chelate was extended to the synthesis and characterization of well-defined Ru(II)-halide complexes. The compound [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] was obtained by simple ligand exchange on the precursor [(PPh3)3RuCl2]. Two isomers were observed by means of 31P{1H} NMR spectroscopy, and were partially separated by recrystallization in refluxing solvents, thus allowing their structure elucidation. X-ray diffraction analysis revealed that the two crystalline isomers have the formula [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] with the phosphite ligand coordinated to the Ru(II) center either in a meridional or in a facial disposition. The mixture [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] undergoes phosphine dissociation at temperatures over 100 °C, leading to the formation of [κ4(P,N3){P(Oquin)3}RuCl2]. This compound displays a tetradentate P(Oquin)3 chelate and is a suitable catalyst for the dehydrogenation of formic acid and the dehydrocoupling of methylphenylsilane.
{"title":"Ruthenium(II) complexes of a tripodal phosphite ligand: Synthesis, characterization, and applications in catalytic dehydrogenation","authors":"","doi":"10.1016/j.ica.2024.122314","DOIUrl":"10.1016/j.ica.2024.122314","url":null,"abstract":"<div><p>The scaffold tris(8-quinolinyl)phosphite, (P(Oquin)<sub>3</sub>), can bind to metal centers as a bi- or a tridentate tripodal ligand, depending on the synthetic conditions and characteristics of the metal atom. Here the study of the coordinating properties of such chelate was extended to the synthesis and characterization of well-defined Ru(II)-halide complexes. The compound [κ<sup>3</sup>(<em>N,P,N</em>){P(Oquin)<sub>3</sub>}RuCl<sub>2</sub>(PPh<sub>3</sub>)] was obtained by simple ligand exchange on the precursor [(PPh<sub>3</sub>)<sub>3</sub>RuCl<sub>2</sub>]. Two isomers were observed by means of <sup>31</sup>P{<sup>1</sup>H} NMR spectroscopy, and were partially separated by recrystallization in refluxing solvents, thus allowing their structure elucidation. X-ray diffraction analysis revealed that the two crystalline isomers have the formula [κ<sup>3</sup>(<em>N,P,N</em>){P(Oquin)<sub>3</sub>}RuCl<sub>2</sub>(PPh<sub>3</sub>)] with the phosphite ligand coordinated to the Ru(II) center either in a <em>meridional</em> or in a <em>facial</em> disposition. The mixture [κ<sup>3</sup>(<em>N,P,N</em>){P(Oquin)<sub>3</sub>}RuCl<sub>2</sub>(PPh<sub>3</sub>)] undergoes phosphine dissociation at temperatures over 100 °C, leading to the formation of [κ<sup>4</sup>(<em>P,N</em><sub><em>3</em></sub>){P(Oquin)<sub>3</sub>}RuCl<sub>2</sub>]. This compound displays a tetradentate P(Oquin)<sub>3</sub> chelate and is a suitable catalyst for the dehydrogenation of formic acid and the dehydrocoupling of methylphenylsilane.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004055/pdfft?md5=217fc3dd8a6a842f6ffd7e8c4088a9d9&pid=1-s2.0-S0020169324004055-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142040198","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 : 2024-08-13DOI: 10.1016/j.ica.2024.122316
A novel binuclear [Zn2(L2C)2(HQ)2] complex with mixed ligands was synthesized using pyrazolone-based derivative (L2C) (1-(3-chlorophenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)(4-nitrophenyl)methanone) as the primary ligand and 8-hydroxyquinoline (8-HQ) as the secondary ligand. Single crystal analysis revealed that each zinc(II) atom is penta-coordinated, involving four O-atoms from two pyrazolone ligands and two N-atoms from the 8-hydroxyquinoline. Two hydroxyl O-atoms from the 8-hydroxyquinoline also bridge the zinc atoms, leading to a distorted square pyramidal geometry. The structure of the complex was further characterized using 1H NMR, FT-IR, UV–vis, TGA, and elemental analysis. The compounds’ electronic behaviour, stable geometry, MEP surfaces, and FMO analysis were studied using density functional theory (DFT) at the B3LYP level with the LanL2DZ basis set. These theoretical results were compared with the experimental structural data of the [Zn2(L2C)2(HQ)2] complex. The complex was tested for its ability to inhibit Plasmodium falciparum in vitro.
以吡唑酮基衍生物 (L2C) (1-(3-chlorophenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)(4-nitrophenyl)methanone) 为主配体,8-羟基喹啉 (8-HQ) 为次配体,合成了一种具有混合配体的新型双核 [Zn2(L2C)2(HQ)2] 复合物。单晶分析表明,每个锌(II)原子都是五配位的,其中四个 O 原子来自两个吡唑酮配体,两个 N 原子来自 8-羟基喹啉。来自 8-羟基喹啉的两个羟基 O 原子也连接了锌原子,从而形成了一个扭曲的正方金字塔几何结构。利用 1H NMR、FT-IR、UV-vis、TGA 和元素分析进一步确定了该复合物的结构。利用密度泛函理论(DFT)和 LanL2DZ 基集,在 B3LYP 水平上对化合物的电子行为、稳定几何形状、MEP 表面和 FMO 分析进行了研究。这些理论结果与 [Zn2(L2C)2(HQ)2] 复合物的实验结构数据进行了比较。测试了该复合物对恶性疟原虫的体外抑制能力。
{"title":"Synthesis, characterization, and crystal features of a mixed ligand binuclear Zinc(II) acyl pyrazolone complex: DFT, Hirshfeld surface analysis and anti-malarial activity evaluation","authors":"","doi":"10.1016/j.ica.2024.122316","DOIUrl":"10.1016/j.ica.2024.122316","url":null,"abstract":"<div><p>A novel binuclear [Zn<sub>2</sub>(L<sub>2</sub>C)<sub>2</sub>(HQ)<sub>2</sub>] complex with mixed ligands was synthesized using pyrazolone-based derivative (L<sub>2</sub>C) (1-(3-chlorophenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)(4-nitrophenyl)methanone) as the primary ligand and 8-hydroxyquinoline (8-HQ) as the secondary ligand. Single crystal analysis revealed that each zinc(II) atom is penta-coordinated, involving four O-atoms from two pyrazolone ligands and two <em>N</em>-atoms from the 8-hydroxyquinoline. Two hydroxyl O-atoms from the 8-hydroxyquinoline also bridge the zinc atoms, leading to a distorted square pyramidal geometry. The structure of the complex was further characterized using <sup>1</sup>H NMR, FT-IR, UV–vis, TGA, and elemental analysis. The compounds’ electronic behaviour, stable geometry, MEP surfaces, and FMO analysis were studied using density functional theory (DFT) at the B3LYP level with the LanL2DZ basis set. These theoretical results were compared with the experimental structural data of the [Zn<sub>2</sub>(L<sub>2</sub>C)<sub>2</sub>(HQ)<sub>2</sub>] complex. The complex was tested for its ability to inhibit <em>Plasmodium falciparum in vitro</em>.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142021295","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}