Pub Date : 2024-11-07DOI: 10.1016/j.poly.2024.117285
Fares Chabira , Toubane Mahdia , Tala-Ighil Razika , Muhammad Humayun , Chun Ouyang , Amal Faleh Alanazi , Mohamed Bououdina , George Z. Kyzas
This study presents an in-depth investigation of zinc oxide hexagonal nanorods (ZnO NRs) synthesized via a hydrothermal approach at three pH basic values conducted in high-pressure laboratory reactor provided by Parr Instrument Company. The research evaluates the catalytic properties of the ZnO NRs, highlighting their potential for environmental applications. The as-fabricated samples are characterized by various techniques including the X-ray diffraction (XRD), UV–visible spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) analysis, Field emission-scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDAX) and high-resolution transmission electron microscopy (HR-TEM). Rietveld refinement of X-ray diffraction data reveals the formation of high-purity hexagonal Wurtzite-type ZnO phase. Further, it is investigated that by decreasing the pH values, the grain size of ZnO NRs increases from 25.70 nm to 29.91 nm. SEM analyses further confirmed the hexagonal nanorod-shaped morphology of ZnO. The photocatalytic degradation performance of the as-fabricated ZnO NRs for Methylene Blue (MB) and Methyl Orange (MO) dyes increased with the increase in pH value, reaching almost 95 % and 64 %, respectively, after 30 min of UV irradiation. The optimum degradation is achieved at a pH value of 11.
{"title":"Exceptional photocatalytic performance of hexagonal ZnO nanorods for anionic and cationic dyes degradation","authors":"Fares Chabira , Toubane Mahdia , Tala-Ighil Razika , Muhammad Humayun , Chun Ouyang , Amal Faleh Alanazi , Mohamed Bououdina , George Z. Kyzas","doi":"10.1016/j.poly.2024.117285","DOIUrl":"10.1016/j.poly.2024.117285","url":null,"abstract":"<div><div>This study presents an in-depth investigation of zinc oxide hexagonal nanorods (ZnO NRs) synthesized via a hydrothermal approach at three pH basic values conducted in high-pressure laboratory reactor provided by Parr Instrument Company. The research evaluates the catalytic properties of the ZnO NRs, highlighting their potential for environmental applications. The as-fabricated samples are characterized by various techniques including the X-ray diffraction (XRD), UV–visible spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) analysis, Field emission-scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDAX) and high-resolution transmission electron microscopy (HR-TEM). Rietveld refinement of X-ray diffraction data reveals the formation of high-purity hexagonal Wurtzite-type ZnO phase. Further, it is investigated that by decreasing the pH values, the grain size of ZnO NRs increases from 25.70 nm to 29.91 nm. SEM analyses further confirmed the hexagonal nanorod-shaped morphology of ZnO. The photocatalytic degradation performance of the as-fabricated ZnO NRs for Methylene Blue (MB) and Methyl Orange (MO) dyes increased with the increase in pH value, reaching almost 95 % and 64 %, respectively, after 30 min of UV irradiation. The optimum degradation is achieved at a pH value of 11.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117285"},"PeriodicalIF":2.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653685","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 : 2024-11-06DOI: 10.1016/j.poly.2024.117287
Samyah D. Jastaniah , S.M. El-Megharbel , Khadeejah Alsolami , Maria N. Alsulami , Najah M. Albaqami , Bander Albogami , Reham Z. Hamza
Background and objective
Minocycline (Mino) is a broad-spectrum antimicrobial that is quickly and fully absorbed. Mino is considered a unique tetracycline derivative. Recently, the number of commercially available antibacterial agents has declined, failing to keep pace with the number of challenges of treating pathogens resistant to multiple drugs. Therefore, it is necessary to develop new classes of antibiotics with different modes of action.
Material and methods
The Mino/manganese (Mino/Mn) complex novel formula was chemically synthesized and fully characterized by using elemental analysis, a lot of spectroscopic methods (infrared (IR), ultraviolet (UV), X-ray diffraction (XRD)), magnetic susceptibility, scanning electron microscopy SEM, and transmission electron microscopy (TEM). The molar conductance value confirmed the non-electrolytic nature of Mino/Mn novel complex. The novel Mino/Mn complex was tested using the ORAC assay and evaluated for its antibacterial activity against the following strains: Escherichia coli (ATCC 8739), Bacillus subtilis (ATCC 6633), Staphylococcus aureus (ATCC 6538), and Klebsiella pneumonia (ATCC 13883).
Results
Spectral data showed that Mino is chelated with Mn(II) via the oxygen atoms through the oxygen of ketonic group (CO) and (-OH) hydroxyl groups. The magnetic moment value confirms the octahedral configuration of the complex. The surface morphology of the novel complex Mino/Mn that was observed via SEM confirmed that the novel complex appeared as small rectangular projections. TEM showed the formation of black spots for Mn(II) chelate with particle sizes in between 9 to 23 nm. The current findings confirmed the high antibacterial activity of the Mino/Mn complex against the four mentioned strains of bacteria at extremely low concentrations: 0.625 mg/ml for E. coli, 0.009 for B. subtilis, and 0.625 for S. aureus. The Mino/Mn complex exhibited potent antioxidant activity by capturing and scavenging free radicals resulting from antibiotic misuse.
Conclusion
Therefore, it can be concluded that the novel formula of the Mino/Mn complex is an effective antioxidant and antibacterial agent with expected high potentially significant biological effects.
{"title":"Spectroscopic and chemical characterization of the novel Minocycline/Mn complex with evaluation of its invitro potent antioxidant activity and high antibacterial effect against Escherichia coli (ATCC 8739), Bacillus subtilis (ATCC6633), Staphylococcus aureus (ATCC 6538), and Klebsiella pneumonia (ATCC 13883)","authors":"Samyah D. Jastaniah , S.M. El-Megharbel , Khadeejah Alsolami , Maria N. Alsulami , Najah M. Albaqami , Bander Albogami , Reham Z. Hamza","doi":"10.1016/j.poly.2024.117287","DOIUrl":"10.1016/j.poly.2024.117287","url":null,"abstract":"<div><h3>Background and objective</h3><div>Minocycline (Mino) is a broad-spectrum antimicrobial that is quickly and fully absorbed. Mino is considered a unique tetracycline derivative. Recently, the number of commercially available antibacterial agents has declined, failing to keep pace with the number of challenges of treating pathogens resistant to multiple drugs. Therefore, it is necessary to develop new classes of antibiotics with different modes of action.</div></div><div><h3>Material and methods</h3><div>The Mino/manganese (Mino/Mn) complex novel formula was chemically synthesized and fully characterized by using elemental analysis, a lot of spectroscopic methods (infrared (IR), ultraviolet (UV), X-ray diffraction (XRD)), magnetic susceptibility, scanning electron microscopy SEM, and transmission electron microscopy (TEM). The molar conductance value confirmed the non-electrolytic nature of Mino/Mn novel complex. The novel Mino/Mn complex was tested using the ORAC assay and evaluated for its antibacterial activity against the following strains: E<em>scherichia coli</em> (ATCC 8739), <em>Bacillus subtilis</em> (ATCC 6633), <em>Staphylococcus aureus</em> (ATCC 6538), and <em>Klebsiella pneumonia</em> (ATCC 13883).</div></div><div><h3>Results</h3><div>Spectral data showed that Mino is chelated with Mn(II) via the oxygen atoms through the oxygen of ketonic group (C<img>O) and (-OH) hydroxyl groups. The magnetic moment value confirms the octahedral configuration of the complex. The surface morphology of the novel complex Mino/Mn that was observed via SEM confirmed that the novel complex appeared as small rectangular projections. TEM showed the formation of black spots for Mn(II) chelate with particle sizes in between 9 to 23 nm. The current findings confirmed the high antibacterial activity of the Mino/Mn complex against the four mentioned strains of bacteria at extremely low concentrations: 0.625 mg/ml for E. coli, 0.009 for <em>B. subtilis</em>, and 0.625 for <em>S. aureus</em>. The Mino/Mn complex exhibited potent antioxidant activity by capturing and scavenging free radicals resulting from antibiotic misuse.</div></div><div><h3>Conclusion</h3><div>Therefore, it can be concluded that the novel formula of the Mino/Mn complex is an effective antioxidant and antibacterial agent with expected high potentially significant biological effects.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117287"},"PeriodicalIF":2.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653687","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}
A copper (II) complex with the asymmetric bidentate Schiff-base ligand (E)-2-(((4-chlorophenyl) imino) methyl) phenol was synthesized and characterized using FTIR and UV–VIS spectroscopy. Photoluminescence studies were conducted on both the copper (II) complex and the free ligand. XRD analysis revealed the copper (II) complex crystallizes in the monoclinic system, space group P21/c. The complex structure was optimized using DFT calculations with B3LYP/6-31G+(d,p) and Lanl2dz basis sets, with QTAIM and NBO analyses confirming complex formation. The energy gap of the copper (II) complex was determined to be 3.701 eV (alpha state) and 2.764 eV (beta state). MEP analysis of the optimized structure indicated a hydrophobic environment around the nitrogen atom, with the molecule exhibiting overall hydrophobicity. The chlorine atoms were identified as potential nucleophilic sites. The antimicrobial efficacy of a Schiff base copper (II) complex was evaluated against selected pathogenic bacteria (B. subtilis, B. megaterum, K. pneumoniae, E. coli) and the fungus Candida albicans. Among these C. albicans for complex showed larger zones (11–15.5 mm) at higher concentrations such as 2 and 2.5 mg/mL. Molecular docking studies suggested strong binding affinity between the complex and the target protein, this was further supported by obtained root means square deviations, root means square fluctuations, radius of gyration and hydrogen bond values during simulations. The binding free energy between BSA and the copper (II) complex was calculated as −8.7 kcal/mol, indicating significant interaction. However, only weak van der Waals interactions were observed between the complex and DNA. Toxicity studies revealed the copper (II) complex had minimal irritant effects on ocular and cutaneous tissues, with a low lethal dose. In comparison, Tricresyl phosphate showed moderate to severe ocular irritancy and modest cutaneous irritancy.
利用傅立叶变换红外光谱和紫外可见分光光度法合成并表征了铜 (II) 与不对称双齿席夫碱配体 (E)-2-(((4-chlorophenyl) imino) methyl) 苯酚的配合物。对铜（II）络合物和游离配体进行了光致发光研究。XRD 分析表明，铜 (II) 复合物为单斜晶系结晶，空间群为 P21/c。利用 B3LYP/6-31G+(d,p) 和 Lanl2dz 基集进行的 DFT 计算优化了络合物结构，QTAIM 和 NBO 分析证实了络合物的形成。铜 (II) 复合物的能隙被确定为 3.701 eV（α态）和 2.764 eV（β态）。对优化结构的 MEP 分析表明，氮原子周围存在疏水环境，分子具有整体疏水性。氯原子被确定为潜在的亲核位点。评估了希夫碱铜 (II) 复合物对某些致病细菌（枯草杆菌、大肠杆菌、肺炎双球菌、大肠杆菌）和真菌白色念珠菌的抗菌效果。其中，在 2 毫克/毫升和 2.5 毫克/毫升等较高浓度下，白念珠菌与复合物的结合区较大（11-15.5 毫米）。分子对接研究表明，复合物与目标蛋白质之间具有很强的结合亲和力，模拟过程中获得的均方根偏差、均方根波动、回旋半径和氢键值进一步证实了这一点。计算得出的 BSA 与铜（II）复合物之间的结合自由能为 -8.7 kcal/mol，表明存在显著的相互作用。然而，在复合物和 DNA 之间只观察到微弱的范德华相互作用。毒性研究表明，铜 (II) 复合物对眼部和皮肤组织的刺激作用很小，致死剂量也很低。相比之下，磷酸三甲苯酯对眼部有中度到严重的刺激作用，对皮肤有轻微的刺激作用。
{"title":"Structural, spectroscopic, and biological properties of an asymmetric Cu (II) Schiff-base complex: Synthesis, DNA/BSA interactions, and antimicrobial potential with experimental and computational insights","authors":"K.J. Rajimon , Rafa Almeer , Pooventhiran Thangaiyan , Renjith Thomas","doi":"10.1016/j.poly.2024.117277","DOIUrl":"10.1016/j.poly.2024.117277","url":null,"abstract":"<div><div>A copper (II) complex with the asymmetric bidentate Schiff-base ligand (E)-2-(((4-chlorophenyl) imino) methyl) phenol was synthesized and characterized using FTIR and UV–VIS spectroscopy. Photoluminescence studies were conducted on both the copper (II) complex and the free ligand. XRD analysis revealed the copper (II) complex crystallizes in the monoclinic system, space group <em>P</em>21/<em>c</em>. The complex structure was optimized using DFT calculations with B3LYP/6-31G+(d,p) and Lanl2dz basis sets, with QTAIM and NBO analyses confirming complex formation. The energy gap of the copper (II) complex was determined to be 3.701 eV (alpha state) and 2.764 eV (beta state). MEP analysis of the optimized structure indicated a hydrophobic environment around the nitrogen atom, with the molecule exhibiting overall hydrophobicity. The chlorine atoms were identified as potential nucleophilic sites. The antimicrobial efficacy of a Schiff base copper (II) complex was evaluated against selected pathogenic bacteria (<em>B. subtilis, B. megaterum, K. pneumoniae, E. coli</em>) and the fungus <em>Candida albicans. Among these C. albicans</em> for complex showed larger zones (11–15.5 mm) at higher concentrations such as 2 and 2.5 mg/mL. Molecular docking studies suggested strong binding affinity between the complex and the target protein, this was further supported by obtained root means square deviations, root means square fluctuations, radius of gyration and hydrogen bond values during simulations. The binding free energy between BSA and the copper (II) complex was calculated as −8.7 kcal/mol, indicating significant interaction. However, only weak van der Waals interactions were observed between the complex and DNA. Toxicity studies revealed the copper (II) complex had minimal irritant effects on ocular and cutaneous tissues, with a low lethal dose. In comparison, Tricresyl phosphate showed moderate to severe ocular irritancy and modest cutaneous irritancy.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117277"},"PeriodicalIF":2.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653691","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 : 2024-11-05DOI: 10.1016/j.poly.2024.117286
Lingli Shao , Youting Fang , Yinjun Diao , Yilin Xue , Shuping Cai , Hui Mao , Duobin Chao
Transition metal complexes are an important class of molecular catalysts for CO2 photoreduction. Herein, we report a bis(terpyridine)Zn(II) complexes modified with anthryl groups. This Zn(II) complex is highly efficient for CO2 photoreduction with a TON of CO up to 585 and 96.2% selectivity, which is 10 times higher than that of its parent complex without any substituent modification. It is further revealed that such a significant enhancement of TON is due to the larger conjugated system of the modified Zn(II) complex, which stabilizes the proposed ligand-based radical anion. These results provide an efficient strategy to enhance the catalytic performance of a molecular catalyst by the ligand modification.
过渡金属配合物是一类重要的二氧化碳光氧化分子催化剂。在此，我们报告了一种用蒽基修饰的双(特吡啶)Zn(II)配合物。这种 Zn(II) 复合物在 CO2 光还原方面具有很高的效率，其 CO 生成吨数可达 585，选择性高达 96.2%，是未进行任何取代基修饰的母体复合物的 10 倍。研究进一步表明，TON 值的如此显著提高是由于修饰后的 Zn(II) 复合物具有更大的共轭体系，从而稳定了拟议的配体基自由基阴离子。这些结果为通过配体修饰提高分子催化剂的催化性能提供了一种有效的策略。
{"title":"An anthryl-modified bis(terpyridine)zinc(II) complex for improved CO2 photoreduction","authors":"Lingli Shao , Youting Fang , Yinjun Diao , Yilin Xue , Shuping Cai , Hui Mao , Duobin Chao","doi":"10.1016/j.poly.2024.117286","DOIUrl":"10.1016/j.poly.2024.117286","url":null,"abstract":"<div><div>Transition metal complexes are an important class of molecular catalysts for CO<sub>2</sub> photoreduction. Herein, we report a bis(terpyridine)Zn(II) complexes modified with anthryl groups. This Zn(II) complex is highly efficient for CO<sub>2</sub> photoreduction with a TON of CO up to 585 and 96.2% selectivity, which is 10 times higher than that of its parent complex without any substituent modification. It is further revealed that such a significant enhancement of TON is due to the larger conjugated system of the modified Zn(II) complex, which stabilizes the proposed ligand-based radical anion. These results provide an efficient strategy to enhance the catalytic performance of a molecular catalyst by the ligand modification.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117286"},"PeriodicalIF":2.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653681","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 : 2024-11-04DOI: 10.1016/j.poly.2024.117283
Leif Kelling, Viktoria H. Gessner
Carbanions are typically highly reactive species but can be efficiently stabilized to even function as stable weakly coordinating anions (WCA). We now report on the coordination chemistry of the recently introduced allyl anion 1, stabilized by ArF (ArF = 3,5-bis(trifluoromethyl)phenyl), triflyl substituents, with various s-block metals. A systematic crystallographic study on the s-block metal salts (Li-Cs, Ca) showed that the alkali metals have minimal impact on the anion, as indicated by the similar structural properties compared to the phosphonium salt of 1. In contrast, the calcium complex showed a slightly more pronounced distortion of the allyl symmetry due to stronger Ca–O interactions with the triflyl group. Additionally, the significance of the allyl moiety in stabilizing the carbanionic charge in 1 was demonstrated by comparing the structural parameters and charge distribution with those of an analogous C1-anion. Overall, these studies confirm the enhanced stability of 1 and its weak coordination tendency.
{"title":"Coordination chemistry of a weakly coordinating carbanion","authors":"Leif Kelling, Viktoria H. Gessner","doi":"10.1016/j.poly.2024.117283","DOIUrl":"10.1016/j.poly.2024.117283","url":null,"abstract":"<div><div>Carbanions are typically highly reactive species but can be efficiently stabilized to even function as stable weakly coordinating anions (WCA). We now report on the coordination chemistry of the recently introduced allyl anion <strong>1</strong>, stabilized by Ar<sup>F</sup> (Ar<sup>F</sup> = 3,5-bis(trifluoromethyl)phenyl), triflyl substituents, with various s-block metals. A systematic crystallographic study on the s-block metal salts (Li-Cs, Ca) showed that the alkali metals have minimal impact on the anion, as indicated by the similar structural properties compared to the phosphonium salt of <strong>1</strong>. In contrast, the calcium complex showed a slightly more pronounced distortion of the allyl symmetry due to stronger Ca–O interactions with the triflyl group. Additionally, the significance of the allyl moiety in stabilizing the carbanionic charge in <strong>1</strong> was demonstrated by comparing the structural parameters and charge distribution with those of an analogous C1-anion. Overall, these studies confirm the enhanced stability of <strong>1</strong> and its weak coordination tendency.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117283"},"PeriodicalIF":2.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653684","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}
Isoniazid-based Schiff base N’-(furan-2-ylmethylene)isonicotinohydrazide (FINH) has been synthesized. FINH has proven its ability to selectively sense and respond to Cu2+, Ni2+, and Hg2+, which shows its potential as a chemosensor. UV–visible experiments, the absorption band (at 360 nm) of FINH shifted with the gradual addition of Cu2+, Ni2+, and Hg2+. A significant quenching in the emission band of FINH in fluorescence spectra has been observed with the addition of analytes at the physiological pH range. Cyclic voltammetric experiments have been conducted to determine the electron transfer process that occurs during the complexation of FINH with analytes. Moreover, the interactions of FINH-metal ions are reversible, and their reversible behavior has been demonstrated with the Na2EDTA solution. The binding insights among FINH and Cu2+, Ni2+, and Hg2+ are explained by IR spectral study. Additionally, the FINH works within the appreciable detection limit of 9.472 x 10−7 M (for Cu2+), 7.685 x 10−7 M (for Ni2+) and 2.411 x 10−7 M (for Hg2+), limit of quantitation of 3.15 x 10−6 M (for Cu2+), 2.561 x 10−6 M (for Ni2+) and 8.036 x 10−7 M (for Hg2+). Applying this isoniazid-based reversible chemosensor in analyzing real samples demonstrates its practicality and effectiveness for multi-analyte detection. This sensor could consistently measure metal ion concentrations in various environmental and biological samples, providing a valuable tool for monitoring pollutants and evaluating exposure risks.
基于异烟肼的希夫碱 N'-（呋喃-2-基亚甲基）异烟酰肼（FINH）已被合成。事实证明，FINH 能够选择性地感知并响应 Cu2+、Ni2+ 和 Hg2+，这显示了其作为化学传感器的潜力。在紫外可见光实验中，随着 Cu2+、Ni2+ 和 Hg2+ 的逐渐加入，FINH 的吸收带（360 纳米）发生了移动。在生理 pH 值范围内，加入分析物后，荧光光谱中 FINH 的发射带明显淬灭。为了确定 FINH 与分析物络合时发生的电子转移过程，我们进行了循环伏安实验。此外，FINH 与金属离子的相互作用是可逆的，其可逆性已在 Na2EDTA 溶液中得到证实。红外光谱研究解释了 FINH 与 Cu2+、Ni2+ 和 Hg2+ 之间的结合关系。此外，FINH 的检测限分别为 9.472 x 10-7 M（Cu2+）、7.685 x 10-7 M（Ni2+）和 2.411 x 10-7 M（Hg2+），定量限分别为 3.15 x 10-6 M（Cu2+）、2.561 x 10-6 M（Ni2+）和 8.036 x 10-7 M（Hg2+）。将这种基于异烟肼的可逆化学传感器应用于实际样品分析，证明了它在多种分析物检测方面的实用性和有效性。这种传感器可持续测量各种环境和生物样本中的金属离子浓度，为监测污染物和评估暴露风险提供了一种宝贵的工具。
{"title":"An Isoniazid-Based reversible Schiff base chemosensor for Multi-Analyte (Cu2+, Ni2+, Hg2+) detection","authors":"Manpreet Kaur , Virender , Ashwani Kumar , Santosh Kumar Dubey","doi":"10.1016/j.poly.2024.117282","DOIUrl":"10.1016/j.poly.2024.117282","url":null,"abstract":"<div><div>Isoniazid-based Schiff base N’-(furan-2-ylmethylene)isonicotinohydrazide (<strong>FINH</strong>) has been synthesized. <strong>FINH</strong> has proven its ability to selectively sense and respond to Cu<sup>2+</sup>, Ni<sup>2+</sup>, and Hg<sup>2+</sup>, which shows its potential as a chemosensor. UV–visible experiments, the absorption band (at 360 nm) of <strong>FINH</strong> shifted with the gradual addition of Cu<sup>2+</sup>, Ni<sup>2+</sup>, and Hg<sup>2+</sup>. A significant quenching in the emission band of <strong>FINH</strong> in fluorescence spectra has been observed with the addition of analytes at the physiological pH range. Cyclic voltammetric experiments have been conducted to determine the electron transfer process that occurs during the complexation of <strong>FINH</strong> with analytes. Moreover, the interactions of <strong>FINH</strong>-metal ions are reversible, and their reversible behavior has been demonstrated with the Na<sub>2</sub>EDTA solution. The binding insights among <strong>FINH</strong> and Cu<sup>2+</sup>, Ni<sup>2+</sup>, and Hg<sup>2+</sup> are explained by IR spectral study. Additionally, the <strong>FINH</strong> works within the appreciable detection limit of 9.472 x 10<sup>−7</sup> M (for Cu<sup>2+</sup>), 7.685 x 10<sup>−7</sup> M (for Ni<sup>2+</sup>) and 2.411 x 10<sup>−7</sup> M (for Hg<sup>2+</sup>), limit of quantitation of 3.15 x 10<sup>−6</sup> M (for Cu<sup>2+</sup>), 2.561 x 10<sup>−6</sup> M (for Ni<sup>2+</sup>) and 8.036 x 10<sup>−7</sup> M (for Hg<sup>2+</sup>). Applying this isoniazid-based reversible chemosensor in analyzing real samples demonstrates its practicality and effectiveness for multi-analyte detection. This sensor could consistently measure metal ion concentrations in various environmental and biological samples, providing a valuable tool for monitoring pollutants and evaluating exposure risks.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117282"},"PeriodicalIF":2.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572219","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 : 2024-10-30DOI: 10.1016/j.poly.2024.117280
Anna G. Matveeva , Margarita P. Pasechnik , Rinat R. Aysin , Tatyana V. Baulina , Anna V. Vologzhanina , Ivan A. Godovikov , Sergey V. Matveev , Igor Yu. Kudryavtsev , Yuri V. Fedorov , Pavel V. Dorovatovskii , Mikhail E. Minyaev , Valery K. Brel
Reaction of tris[2-(2′-pyridylmethoxy)phenyl]phosphine oxide (L) with f-element nitrates resulted in 1:1 complexes. The isolated complexes of ligand L with La(III), Eu(III), Tb(III), and U(VI) nitrates, and with La(III) chloride were studied in the solid state and solution by IR, Raman, and NMR spectroscopy, X-ray analysis, and also DFT calculations. Composition and structure of the complexes vary with lanthanide cation radius. According to the data of elemental analysis, vibrational spectroscopy, and X-ray diffraction, the ligand is coordinated in tridentate mode in crystalline La(III) and solid Eu(III) complexes: [Ln(OPO,N,Oeth-L)(H2O)(O,O-NO3)3], and in monodentate mode in crystalline complex [Tb(OPO-L)(H2O)2(O,O-NO3)3]. Nitrogen atoms of pyridine fragments of the ligand not involved in coordination produce intra- and intermolecular H-bonds with coordinated water molecules in the second coordination sphere of Ln(III). According to IR, NMR spectrometry, and DFT calculations, the structure of coordination polyhedron of the main species of Ln(III) complexes in acetonitrile solutions is retained including coordination of one of pyridine fragments in the second coordination sphere: [Ln{OPO,N,(N*),Oeth-L}(H2O)(O,O-NO3)3] and [Tb{OPO,(N*)-L}(H2O)2(O,O-NO3)3], where Ln = La, Eu, and N* is the nitrogen atom of pyridine fragment producing intramolecular H-bond with coordinated water molecule. According IR and Raman spectroscopy, ligand L is coordinated in bidentate mode in solid complex [UO2(OPO,N-L)(O,O-NO3)], and uncoordinated nitrogen atoms remain free. Solution structure of uranyl complex is labile and depends on solvent nature. Equilibria of complex species with variable coordination of nitrate ions, ligand L, and with probable involvement of water take place in CD3CN and CDCl3 solutions. Photophysical properties of the prepared Eu(III) and Tb(III) complexes were studied. The preliminary assessment of extraction properties of compound L was made. Stability of studied compounds in acetonitrile solutions was examined, and the structure of one of protolysis product of Eu(III) complex, [Eu(LH)(H2O)(NO3)4], was established by micro-IR and X-ray analysis.
三[2-(2′-吡啶基甲氧基)苯基]氧化膦（L）与 f 元素硝酸盐反应生成 1:1 的络合物。通过红外光谱、拉曼光谱、核磁共振光谱、X 射线分析以及 DFT 计算，研究了配体 L 与 La(III)、Eu(III)、Tb(III) 和 U(VI) 硝酸盐以及 La(III) 氯化物在固态和溶液中的分离配合物。配合物的组成和结构随镧系阳离子半径的变化而变化。根据元素分析、振动光谱和 X 射线衍射数据，配体在结晶 La(III) 和固体 Eu(III) 复合物 [Ln(OPO,N,Oeth-L)(H2O)(O,O-NO3)3] 中以三叉配位模式配位，在结晶复合物 [Tb(OPO-L)(H2O)2(O,O-NO3)3] 中以单配位模式配位。配体中不参与配位的吡啶片段的氮原子与 Ln(III) 第二配位圈中的配位水分子产生分子内和分子间 H 键。根据红外光谱、核磁共振光谱和 DFT 计算，Ln(III) 复合物主要种类在乙腈溶液中的配位多面体结构得以保留，包括其中一个吡啶片段在第二配位层中的配位：[Ln{OPO,N,(N*),Oeth-L}(H2O)(O,O-NO3)3]和[Tb{OPO,(N*)-L}(H2O)2(O,O-NO3)3]，其中 Ln = La、Eu，N* 是吡啶片段的氮原子，与配位水分子产生分子内 H 键。根据红外光谱和拉曼光谱，配体 L 在固体配合物 [UO2(OPO,N-L)(O,O-NO3)]中以双配位方式配位，未配位的氮原子保持自由状态。铀酰络合物的溶液结构是易变的，取决于溶剂的性质。在 CD3CN 和 CDCl3 溶液中，硝酸根离子和配体 L 的配位各不相同，而且可能有水的参与。研究了制备的 Eu（III）和 Tb（III）配合物的光物理特性。对化合物 L 的萃取特性进行了初步评估。考察了所研究化合物在乙腈溶液中的稳定性，并通过显微红外和 X 射线分析确定了 Eu（III）络合物的一种原分解产物[Eu(LH)(H2O)(NO3)4]的结构。
{"title":"Solution and solid state structures of lanthanides(III) and uranyl(II) complexes of tripodal tris(2-pyridyl)-containing ligand on Ph3P(O) platform","authors":"Anna G. Matveeva , Margarita P. Pasechnik , Rinat R. Aysin , Tatyana V. Baulina , Anna V. Vologzhanina , Ivan A. Godovikov , Sergey V. Matveev , Igor Yu. Kudryavtsev , Yuri V. Fedorov , Pavel V. Dorovatovskii , Mikhail E. Minyaev , Valery K. Brel","doi":"10.1016/j.poly.2024.117280","DOIUrl":"10.1016/j.poly.2024.117280","url":null,"abstract":"<div><div>Reaction of tris[2-(2′-pyridylmethoxy)phenyl]phosphine oxide (<strong>L</strong>) with <em>f</em>-element nitrates resulted in 1:1 complexes. The isolated complexes of ligand <strong>L</strong> with La(III), Eu(III), Tb(III), and U(VI) nitrates, and with La(III) chloride were studied in the solid state and solution by IR, Raman, and NMR spectroscopy, X-ray analysis, and also DFT calculations. Composition and structure of the complexes vary with lanthanide cation radius. According to the data of elemental analysis, vibrational spectroscopy, and X-ray diffraction, the ligand is coordinated in tridentate mode in crystalline La(III) and solid Eu(III) complexes: [Ln(O<sub>PO</sub>,N,O<sub>eth</sub>-<strong>L</strong>)(H<sub>2</sub>O)(O,O-NO<sub>3</sub>)<sub>3</sub>], and in monodentate mode in crystalline complex [Tb(O<sub>PO</sub>-<strong>L</strong>)(H<sub>2</sub>O)<sub>2</sub>(O,O-NO<sub>3</sub>)<sub>3</sub>]. Nitrogen atoms of pyridine fragments of the ligand not involved in coordination produce intra- and intermolecular H-bonds with coordinated water molecules in the second coordination sphere of Ln(III). According to IR, NMR spectrometry, and DFT calculations, the structure of coordination polyhedron of the main species of Ln(III) complexes in acetonitrile solutions is retained including coordination of one of pyridine fragments in the second coordination sphere: [Ln{O<sub>PO</sub>,N,(N*),O<sub>eth</sub>-<strong>L</strong>}(H<sub>2</sub>O)(O,O-NO<sub>3</sub>)<sub>3</sub>] and [Tb{O<sub>PO</sub>,(N*)-<strong>L</strong>}(H<sub>2</sub>O)<sub>2</sub>(O,O-NO<sub>3</sub>)<sub>3</sub>], where Ln = La, Eu, and N* is the nitrogen atom of pyridine fragment producing intramolecular H-bond with coordinated water molecule. According IR and Raman spectroscopy, ligand <strong>L</strong> is coordinated in bidentate mode in solid complex [UO<sub>2</sub>(O<sub>PO</sub>,<em>N</em>-<strong>L</strong>)(O,O-NO<sub>3</sub>)], and uncoordinated nitrogen atoms remain free. Solution structure of uranyl complex is labile and depends on solvent nature. Equilibria of complex species with variable coordination of nitrate ions, ligand <strong>L</strong>, and with probable involvement of water take place in CD<sub>3</sub>CN and CDCl<sub>3</sub> solutions. Photophysical properties of the prepared Eu(III) and Tb(III) complexes were studied. The preliminary assessment of extraction properties of compound <strong>L</strong> was made. Stability of studied compounds in acetonitrile solutions was examined, and the structure of one of protolysis product of Eu(III) complex, [Eu(<strong>L</strong>H)(H<sub>2</sub>O)(NO<sub>3</sub>)<sub>4</sub>], was established by micro-IR and X-ray analysis.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117280"},"PeriodicalIF":2.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593097","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 : 2024-10-28DOI: 10.1016/j.poly.2024.117281
Abdulbasit Anoze Aliyu , Joshua Ayoola Obaleye , Abdullahi Ola Rajee , Rawlings A. Timothy , Favour A. Nelson , Monu Joy
A novel mixed ligand Cd(II) complex [Cd(nap)2(imd)3] bearing naproxen and imidazole ligands have been synthesized. Characterization of the mono-nuclear complex was carried out via: 1H & 13C NMR, FTIR, UV–vis and MS and the structure validated with SC-XRD studies. The complex forms a monoclinic crystal structure with space group P21 and a = 13.581(8) Å, b = 8.290(5) Å, c = 16.693(10) Å, a = γ = 90°, b = 109.352(18)°,V = 1773.1(18) Å3. FTIR data confirmed the binding of the naproxenato ligand via the deprotonated oxygen atom to the cadmium (II) ion. The coordination sphere around the Cd(II) center is a 7-coordinate system with a distorted pentagonal bipyramidal geometry having a CdN3O4 chromophore with bidentate ligation of the carboxylate ligand naproxen. Docking with the ADP-ribosyl transferase binding component protein (PDB: 6v1s) gave a binding affinity of −9.8 kcal/mol for the complex [Cd(nap)2(imd)3], establishing eight hydrogen bonds, with the shortest bond length observed in serine. It exhibited greater binding affinity (−9.5 kcal/mol) and established a higher number of hydrogen bonds compared to azithromycin. Tyrosine A:100 exhibited the shortest bond length among the six hydrogen bond interactions detected during docking with prostaglandin reductase 2 (PDB: 2zb7), resulting in a binding affinity of −8.6 kcal/mol. In comparison, ibuprofen demonstrated lower binding affinity (−7.6 kcal/mol) and formed fewer hydrogen bonds. Overall, molecular docking results strongly suggest that [Cd(nap)2(imd)3] exhibits high binding affinities with both ADP-ribosyltransferase binding component and prostaglandin reductase 2, indicating its potential as a candidate for treating bacterial infections and inflammation. The complex exhibited higher radical scavenging activity than the unbound ligands but was less than the ascorbic acid standard in the in-vitro antioxidant experiment. The complex showed promising inhibitory action against some bacterial and fungal strains. The current results may be due to the combined impact of the ligands and the metal ion during complex formation.
{"title":"Novel Cd(II) complex bearing naproxen and imidazole ligands: Synthesis, single-crystal X-ray, structural elucidation, quantum chemical investigation, molecular docking, antioxidant and antimicrobial screening","authors":"Abdulbasit Anoze Aliyu , Joshua Ayoola Obaleye , Abdullahi Ola Rajee , Rawlings A. Timothy , Favour A. Nelson , Monu Joy","doi":"10.1016/j.poly.2024.117281","DOIUrl":"10.1016/j.poly.2024.117281","url":null,"abstract":"<div><div>A novel mixed ligand Cd(II) complex [Cd(nap)<sub>2</sub>(imd)<sub>3</sub>] bearing naproxen and imidazole ligands have been synthesized. Characterization of the mono-nuclear complex was carried out via: <sup>1</sup>H & <sup>13</sup>C NMR, FTIR, UV–vis and MS and the structure validated with SC-XRD studies. The complex forms a monoclinic crystal structure with space group <em>P</em><sub>21</sub> and a = 13.581(8) Å, b = 8.290(5) Å, c = 16.693(10) Å, a = γ = 90°, b = 109.352(18)°,V = 1773.1(18) Å<sup>3</sup>. FTIR data confirmed the binding of the naproxenato ligand via the deprotonated oxygen atom to the cadmium (II) ion. The coordination sphere around the Cd(II) center is a 7-coordinate system with a distorted pentagonal bipyramidal geometry having a CdN<sub>3</sub>O<sub>4</sub> chromophore with bidentate ligation of the carboxylate ligand naproxen. Docking with the ADP-ribosyl transferase binding component protein (PDB: 6v1s) gave a binding affinity of −9.8 kcal/mol for the complex [Cd(nap)<sub>2</sub>(imd)<sub>3</sub>], establishing eight hydrogen bonds, with the shortest bond length observed in serine. It exhibited greater binding affinity (−9.5 kcal/mol) and established a higher number of hydrogen bonds compared to azithromycin. Tyrosine A:100 exhibited the shortest bond length among the six hydrogen bond interactions detected during docking with prostaglandin reductase 2 (PDB: 2zb7), resulting in a binding affinity of −8.6 kcal/mol. In comparison, ibuprofen demonstrated lower binding affinity (−7.6 kcal/mol) and formed fewer hydrogen bonds. Overall, molecular docking results strongly suggest that [Cd(nap)<sub>2</sub>(imd)<sub>3</sub>] exhibits high binding affinities with both ADP-ribosyltransferase binding component and prostaglandin reductase 2, indicating its potential as a candidate for treating bacterial infections and inflammation. The complex exhibited higher radical scavenging activity than the unbound ligands but was less than the ascorbic acid standard in the in-vitro antioxidant experiment. The complex showed promising inhibitory action against some bacterial and fungal strains. The current results may be due to the combined impact of the ligands and the metal ion during complex formation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117281"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571759","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 : 2024-10-28DOI: 10.1016/j.poly.2024.117278
Liping Chen , Shuaicong Huo , Piao Wang , Xuyan Bai , Yujia Gao , Ying Yang
A series of four new bis(imino)phosphine [NPN] ligands PhP(C6H4-2-HC=NAr)2 (Ar = 4-OMeC6H4 (L1, 1), 4-ClC6H4 (L2, 2), 4-BrC6H4 (L3, 3), 2,6-iPr2C6H3 (L4, 4)) were synthesized and structurally characterized. Their reactions with Cu(I) halides CuX (X = Cl, Br, I) were explored for the assembly of coordination complexes LnCuX, and the effects of substituent (Ar) and anion (X) were also investigated in a comparative manner. It was found that the reaction of methoxy substituted L1 (Ar = 4-OMeC6H4) with CuX gave the mononuclear Cu(I) complexes L1CuX (X = Cl (1a), Br (1b), I (1c)) with isostructural feature. In contrast, when halogen-substituted ligands L2-3 (4-ClC6H4, 4-BrC6H4) were applied, their reactions with CuCl afforded the formation of tetranuclear dimer [Ln(CuCl)2]2 (n = 2 (2a), 3 (3a)) bridged by the Cu2Cl2 square, regardless of the composition of the reactants. On the other hand, reactions of L2-3 with CuBr and CuI generated the mononuclear Cu(I) complexes LnCuX (n = 2, X = Br (2b), I (2c); n = 3, X = Br (3b), I (3c)) again. In all these cases above, L1-3 ligands played the tridentate role by biting the copper(I) centers through NPN sites. When the bulky L4 (Ar = 2,6-iPr2C6H3) was involved, the binuclear dimer (L4CuI)2 (4c) bridged by iodide anions was obtained, where each L4 ligand coordinated the copper center using the bidentate P^N mode with another imino arm pendant. In further exploration, 1,10-o-phenanthroline (denoted as phen) was introduced to produce the heteroleptic complex L1CuCl(phen) (1d), where both imino arms in L1 were pendent. The obtained ligand (L1-4) and Cu(I) complexes were characterized by melting point, elemental analysis, FT-IR, UV–Vis, NMR, and single crystal X-ray diffraction.
{"title":"Synthesis and characterization of Bis(imino)phosphine [NPN] ligands and their copper(I) halide complexes","authors":"Liping Chen , Shuaicong Huo , Piao Wang , Xuyan Bai , Yujia Gao , Ying Yang","doi":"10.1016/j.poly.2024.117278","DOIUrl":"10.1016/j.poly.2024.117278","url":null,"abstract":"<div><div>A series of four new bis(imino)phosphine [NPN] ligands PhP(C<sub>6</sub>H<sub>4</sub>-2-HC=NAr)<sub>2</sub> (Ar = 4-OMeC<sub>6</sub>H<sub>4</sub> (L<sup>1</sup>, <strong>1</strong>), 4-ClC<sub>6</sub>H<sub>4</sub> (L<sup>2</sup>, <strong>2</strong>), 4-BrC<sub>6</sub>H<sub>4</sub> (L<sup>3</sup>, <strong>3</strong>), 2,6-<em>i</em>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub> (L<sup>4</sup>, <strong>4</strong>)) were synthesized and structurally characterized. Their reactions with Cu(I) halides CuX (X = Cl, Br, I) were explored for the assembly of coordination complexes L<em><sup>n</sup></em>CuX, and the effects of substituent (Ar) and anion (X) were also investigated in a comparative manner. It was found that the reaction of methoxy substituted L<sup>1</sup> (Ar = 4-OMeC<sub>6</sub>H<sub>4</sub>) with CuX gave the mononuclear Cu(I) complexes L<sup>1</sup>CuX (X = Cl (<strong>1a</strong>), Br (<strong>1b</strong>), I (<strong>1c</strong>)) with isostructural feature. In contrast, when halogen-substituted ligands L<sup>2-3</sup> (4-ClC<sub>6</sub>H<sub>4</sub>, 4-BrC<sub>6</sub>H<sub>4</sub>) were applied, their reactions with CuCl afforded the formation of tetranuclear dimer [L<em><sup>n</sup></em>(CuCl)<sub>2</sub>]<sub>2</sub> (n = 2 (<strong>2a</strong>), 3 (<strong>3a</strong>)) bridged by the Cu<sub>2</sub>Cl<sub>2</sub> square, regardless of the composition of the reactants. On the other hand, reactions of L<sup>2-3</sup> with CuBr and CuI generated the mononuclear Cu(I) complexes L<em><sup>n</sup></em>CuX (n = 2, X = Br (<strong>2b</strong>), I (<strong>2c</strong>); n = 3, X = Br (<strong>3b</strong>), I (<strong>3c</strong>)) again. In all these cases above, L<sup>1-3</sup> ligands played the tridentate role by biting the copper(I) centers through NPN sites. When the bulky L<sup>4</sup> (Ar = 2,6-<em>i</em>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) was involved, the binuclear dimer (L<sup>4</sup>CuI)<sub>2</sub> (<strong>4c</strong>) bridged by iodide anions was obtained, where each L<sup>4</sup> ligand coordinated the copper center using the bidentate P^N mode with another imino arm pendant. In further exploration, 1,10-<em>o</em>-phenanthroline (denoted as phen) was introduced to produce the heteroleptic complex L<sup>1</sup>CuCl(phen) (<strong>1d</strong>), where both imino arms in L<sup>1</sup> were pendent. The obtained ligand (L<sup>1-4</sup>) and Cu(I) complexes were characterized by melting point, elemental analysis, FT-IR, UV–Vis, NMR, and single crystal X-ray diffraction.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117278"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561317","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 : 2024-10-28DOI: 10.1016/j.poly.2024.117272
Milagrina D’Souza , Nikita N. Harmalkar , Vishnu R. Chari , Beena K. Vernekar , Sunder N. Dhuri
Four new organic ammonium tetrasulfidometallates: (4-aminopyridinium)2[MoS4]·H2O 1, (4-aminopyridinium)2[WS4]·H2O 2, (2-amino-6-methylpyridinium)2[MoS4] 3, and (2-amino-6-methylpyridinium)2[WS4] 4 have been synthesized by a well-known base promoted cation exchange method. All compounds were characterized by elemental analysis, IR/Raman/UV–Vis spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structures of 1 and 2 consist of unique tetrahedral [MoS4]2− and [WS4]2− dianions, which are charge-balanced by crystallographically independent 4-aminopyridinium monocations. Additionally, both have a lattice water molecule, which contributes to the overall stability of their structures. In compounds 3 and 4, 4-aminopyridinium of 1 and 2 are replaced by 2-amino-6-methylpyridinium cation and lack lattice water. The different H-bonding interactions viz NH⋯S, CH⋯S, NH⋯O and OH⋯O are observed in 1 and 2, which are reduced to two viz. NH⋯S and CH⋯S in 3 and 4. The weak interactions (NH⋯O and OH⋯O) originating from lattice water further interlink cations with [MoS4]2− and [WS4]2− anions forming extended networks in 1 and 2. To understand the importance of intermolecular interactions in the structures of 1–4, the Hirshfeld surface analyses were performed. The enrichment ratio (E) in the structures of compounds 1–4 was obtained. Compounds 1–4 were tested for their sulfur transfer ability. Only compound 1 showed a predominant disulfide product formation in reaction with 1,3-dibromopropane.
{"title":"Bis(4-aminopyridinium) and bis(2-amino-6-methylpyridinium) cations stabilised by [MS4]2− anions: Synthesis, crystal structures, Hirshfeld surface analysis and sulfur transfer reactions","authors":"Milagrina D’Souza , Nikita N. Harmalkar , Vishnu R. Chari , Beena K. Vernekar , Sunder N. Dhuri","doi":"10.1016/j.poly.2024.117272","DOIUrl":"10.1016/j.poly.2024.117272","url":null,"abstract":"<div><div>Four new organic ammonium tetrasulfidometallates: (4-aminopyridinium)<sub>2</sub>[MoS<sub>4</sub>]·H<sub>2</sub>O <strong>1</strong>, (4-aminopyridinium)<sub>2</sub>[WS<sub>4</sub>]·H<sub>2</sub>O <strong>2</strong>, (2-amino-6-methylpyridinium)<sub>2</sub>[MoS<sub>4</sub>] <strong>3</strong>, and (2-amino-6-methylpyridinium)<sub>2</sub>[WS<sub>4</sub>] <strong>4</strong> have been synthesized by a well-known base promoted cation exchange method. All compounds were characterized by elemental analysis, IR/Raman/UV–Vis spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structures of <strong>1</strong> and <strong>2</strong> consist of unique tetrahedral [MoS<sub>4</sub>]<sup>2−</sup> and [WS<sub>4</sub>]<sup>2−</sup> dianions, which are charge-balanced by crystallographically independent 4-aminopyridinium monocations. Additionally, both have a lattice water molecule, which contributes to the overall stability of their structures. In compounds <strong>3</strong> and <strong>4</strong>, 4-aminopyridinium of <strong>1</strong> and <strong>2</strong> are replaced by 2-amino-6-methylpyridinium cation and lack lattice water. The different H-bonding interactions <em>viz N</em><img><em>H</em>⋯<em>S</em>, <em>C</em><img><em>H</em>⋯<em>S</em>, <em>N</em><img><em>H</em>⋯<em>O</em> and <em>O</em><img><em>H</em>⋯<em>O</em> are observed in <strong>1</strong> and <strong>2</strong>, which are reduced to two <em>viz. N</em><img><em>H</em>⋯<em>S</em> and <em>C</em><img><em>H</em>⋯<em>S</em> in <strong>3</strong> and <strong>4</strong>. The weak interactions (<em>N</em><img><em>H</em>⋯<em>O</em> and <em>O</em><img><em>H</em>⋯<em>O</em>) originating from lattice water further interlink cations with [MoS<sub>4</sub>]<sup>2−</sup> and [WS<sub>4</sub>]<sup>2−</sup> anions forming extended networks in <strong>1</strong> and <strong>2</strong>. To understand the importance of intermolecular interactions in the structures of <strong>1</strong>–<strong>4</strong>, the Hirshfeld surface analyses were performed. The enrichment ratio (E) in the structures of compounds <strong>1</strong>–<strong>4</strong> was obtained. Compounds <strong>1</strong>–<strong>4</strong> were tested for their sulfur transfer ability. Only compound <strong>1</strong> showed a predominant disulfide product formation in reaction with 1,3-dibromopropane.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117272"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561316","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}
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