Applied Organometallic Chemistry最新文献

Two novel multifunctional complexes [M(CCAM)₂(NO₃)](NO₃)₂·C₂H₅OH (M = Dy (III)/Er (III); CCAM = 2-cyano-N′-((4-oxo-4H-chromen-3-yl)methylene)acetohydrazide) were synthesized and characterized via elemental and thermal analyses, molar conductivity, UV–vis., and FT-IR spectroscopy, revealing a 1:2 metal-to-ligand stoichiometry. The CCAM ligand coordinated with Dy(III) or Er(III) ions through nitrogen of azomethine and oxygen of the carbonyl and γ-pyran groups. Corrosion inhibition studies for Dy(CCAM), Er(CCAM), and CCAM on carbon steel (C-steel) in 1-M HCl showed Dy(CCAM) and Er(CCAM) as highly efficient, with Er(CCAM) offering the best protection. In a 1-M HCl solution, Fe²⁺ at the C-steel surface interacts with the CCAM, Dy(CCAM), and Er(CCAM) compounds, as demonstrated by UV–vis spectroscopy. At a concentration of 10⁻³ M, the Dy(CCAM) and Er(CCAM) compounds showed greater performance efficiency in the weight loss test in 1-M HCl solution, reaching 93.34% and 95.67%, respectively. The Langmuir adsorption isotherm pronounced the mixed adsorption mechanisms. The surface characteristics SEM, EDX, AFM, and contact angle measurements confirmed surface shielding. In vitro antibacterial and antifungal activity of the prepared compounds against organisms, including Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis as bacteria, and Candida albicans and Aspergillus fumigatus as fungi is carried out. Er(CCAM) inhibitor exhibits the greatest action against different tested antimicrobials. Additionally, the in vitro cytotoxicity of the produced complexes as growth inhibitory effects against Erlish Acities Carcinoma was ascertained. Er(CCAM) and Dy(CCAM) were found to have cytotoxic levels with (IC₅₀ of 64 and 65 μM), respectively. As a result, Er(CCAM) inhibitor is a more effective therapeutic approach for the creation of novel antimicrobial and antitumor agents. For Er(CCAM) superior corrosion protection, the theoretical studies of molecular docking and DFT and MD simulations validated the experimental results.

A cube-like heptanuclear cobalt(II) cluster single crystals, namely, [Co₇(L)₂(μ₃-OCH₃)₂(μ₃-OH)₄](ClO₄)₂, was successfully grown up by reacting of a bis(salamo)-type ligand H₃L containing two N₂O₂ coordination cavities with Co(NO₃)₂·6H₂O using natural volatilization method. Single-crystal analysis displayed that the cobalt(II) cluster is a heptanuclear cobalt(II) cluster. In this paper, the UV–Vis absorption and fluorescence spectra of H₃L and its cobalt(II) cluster have been investigated. Through Hirshfeld surface analyses, the intermolecular interactions on the molecular surfaces are visually presented, and the contributions of each interaction to the intermolecular surface interactions are quantified by two-dimensional fingerprints. DFT calculation and MEP analyses have been used to investigate the electronic structures and coordination sites of the cobalt(II) cluster.

The oxidative transformation of sulfides to sulfoxides over magnetic green catalysts is one of the most important applications in pharmaceuticals. In this report, we demonstrate the step-by-step fabrication and synthesis of CoFe₂O₄, CuFe₂O₄, and Fe₃O₄ nanocomposite modified with orange peel extract complexes as advanced high-performance magnetic nanocomposite materials. One of the goals of this project was to use phenolic acid phytochemicals in the catalytic process. The newly synthesized nanocomposites were characterized by several advanced analytical methods. Utilizing the Box–Behnken experimental design and the response surface methodology (RSM), reaction parameters such the amount of catalyst, hydrogen peroxide, and duration were improved. Furthermore, without experiencing a discernible loss of reactivity in the sulfide oxidation reaction, the catalysts were effortlessly magnetically retrieved and may be employed repeatedly.

As the amount of tetrachlorobisphenol A (TCBPA) that causes potential adverse effects on human health in the environment is continually increasing. It is therefore important to develop new materials for the adsorption or degradation of these compounds using various techniques. In this study, two novel magnetic recyclable composite catalysts Zr–NiFe₂O₄@ZIF-67 and Zr–NiFe₂O₄@ZIF-8 were synthesized. These catalysts degraded tetrachlorobisphenol A (TCBPA) in water by activating peroxydisulfate (PDS)/peroxymonosulfate (PMS), respectively. The results show that the Zr–NiFe₂O₄@ZIF-67-5%/LED/(NH₄)₂S₂O₈ system can degrade 95% of TCBPA (20 mg/L) within 30 min, whereas the Zr–NiFe₂O₄@ZIF-8-10%/LED/KHSO₅ system degrades 90% of TCBPA within 30 min. In instances of metal leaching at low concentrations, nickel and iron ions declined to 0.008 mg·L⁻¹, TCBPA exhibits highly efficient and sustainable catalytic properties, maintaining over 80% efficacy across six cycles. The online infrared test experiment results showed the major functional groups disappearing within approximately 130 s. The results of electron paramagnetic resonance and free-radical-quenching experiments showed that SO₄˙⁻, ˙OH, ¹O₂, and O₂˙⁻ were involved in the degradation of TCBPA. The possible degradation paths are isomerization polymerization, dechlorination, hydroxylation, ring-opening by oxidation, and further transformation into small molecules of acids, aldehydes, alcohols and other compounds. Thus, in this study, a reliable technique for the degradation of halogenated bisphenol compounds is developed. Overall, the photocatalytic degradation of organic pollutants in water utilizing polymetallic composites as catalysts represents an innovative approach to water treatment, demonstrating enhanced catalytic activity and recyclability, with promising prospects for significant advancements in both theoretical research and practical applications.

We report a direct and efficient methodology for the hydroboration of aliphatic and aryl nitro compounds using amidophosphine-borane {(C₆H₅)CH₂N(PPh)₂(BH₃)₂} in the presence of iron(II) chloride as a catalyst under mild conditions to form primary amines after hydrolysis. Solid amidophosphine-boranes are user-friendly and readily synthesized, revealing remarkable reducing properties toward a comprehensive range of nitro compounds. The scalability of the present approach is defined by performing gram-scale reactions and synthesis of different pharmaceuticals like paracetamol and benzocaine, demonstrating the synthetic applicability of the current strategy.

The construction and optimization of an effective photocatalyst for photodegradation of persistent recalcitrant organic remains challenging. In this work, MIL-101(Cr)-based nanocomposites (AgI@MCr) are proposed to be fabricated by a simple, green solvent, and room temperature in situ preparation strategy, achieving a highly efficient photocatalytic degradation of organic dye rhodamine B (RhB) molecule under visible light irradiation. Extensive characterization (XRD, FTIR, N₂ adsorption–desorption, SEM and EDS, TG, XPS, UV–vis DRS, PL, transient photocurrent, and EIS) confirmed the composite material's structure, morphology, elemental composition, and optical characteristics. Among all the prepared nanocomposites, AgI@MCr-2 demonstrates outstanding photocatalytic performance for RhB with a removal efficiency of 95.4% within 70 min, and a reaction kinetics of 0.0392 min⁻¹, superior to pristine AgI or MIL-101(Cr), and also shows excellent durability, retaining over 80% RhB degradation efficiency after four cycles. Remarkably, the significant enhancement is attributed to the built interfacial contact and synergistic effect between substances in the nanocomposite, high specific surface area, strong visible light–harvesting capacity, low bandgaps, and high electron–hole pair separation. In addition, a possible degradation route for the AgI@MCr nanocomposite is further proposed using various analysis techniques. This study provides valuable references for developing effective multicomponent MOF-based photocatalytic composite materials for dyeing wastewater treatment and environmental remediation.

This study presents the synthesis, characterization, and bioevaluation of novel water-soluble nickel (NiMNPSCA) and copper (CuMNPSCA) mixed-ligand complexes. The complexes were synthesized in aqueous media using Ni (II) or Cu (II), sodium salicylate (SCA), and a Schiff base derived from 2-hydroxy naphthaldehyde (MNP). Comprehensive characterization was achieved using UV–vis, IR spectroscopy, mass spectrometry, elemental analysis, and thermal and magnetic techniques. Both complexes exhibited exceptional thermal stability (melting points > 300°C), water solubility, and 1:1 electrolyte behavior. Structurally, NiMNPSCA adopts a tetrahedral geometry, while CuMNPSCA features an octahedral arrangement. Quantum chemical analyses revealed a narrower energy gap (ΔE = 3.06 eV) and a higher electrophilicity index (ω = 9.66) for CuMNPSCA, suggesting superior chemical reactivity and biological potential. Both complexes demonstrated significantly enhanced antibacterial, antifungal, and anti-inflammatory activities compared to their free ligands, with CuMNPSCA showing efficacy comparable to standard agents in both antimicrobial and anti-inflammatory applications. Notably, CuMNPSCA exhibited potent anti-inflammatory activity, achieving the highest inhibition rate and an IC₅₀ value competitive with ibuprofen. Molecular docking studies reinforced these findings, highlighting the strong binding affinities of CuMNPSCA to dihydropteroate synthase (DHPS, PDB ID: 5JQ9; −8.00 kcal/mol), cyclooxygenase (COX, PDB ID: 6COX; −9.80 kcal/mol), and the SARS-CoV-2 main protease (Mpro, PDB ID: 6LU7; −7.60 kcal/mol). Detailed interaction analysis revealed that metal coordination significantly enhanced the complexes' stability and binding efficacy through hydrogen bonds, π-π stacking, and π-cation interactions. This work positions NiMNPSCA and CuMNPSCA as highly promising candidates for antimicrobial, antifungal, and anti-inflammatory drug development, with CuMNPSCA emerging as a standout compound with strong therapeutic potential. Its multifaceted bioactivity, combined with robust structural stability and reactivity, underscores its potential as a versatile therapeutic agent, particularly in antimicrobial resistance and anti-COVID-19 strategies.

The synthesis, characterizations, and tyrosinase enzyme inhibition experiments on eight novel lanthanide metal complexes (1–8) are reported. A multidonor versatile ligand L was prepared from the condensation reaction of picolinohydrazide with pyridoxal. The synthesized complexes were analyzed using FT-IR and UV-vis spectroscopies, elemental (CHN) analysis, and single-crystal X-ray diffraction analysis. These complexes exhibited significant tyrosinase enzyme inhibition with IC₅₀ values in the range of 9.67 ± 0.17–21.88 ± 0.57 μM. The molecular docking results of the most active complex (2) correlate well with in vitro observations.

Nickel (II) ions (Ni (II)) doped into the zinc-based metal–organic framework Zn-BDC have shown exceptional catalytic activity as heterogeneous catalysts for the three-component Biginelli condensation reaction, delivering yields ranging from 62% to 96% with excellent selectivity under diverse reaction conditions. The Ni doping was achieved through a facile solvothermal synthesis, producing Ni(x)-Zn-BDC catalysts, where x represents the weight percentage of Ni relative to Zn (e.g., Ni[10]-Zn-BDC). Comprehensive characterization of the synthesized catalysts was conducted using advanced spectroscopic and analytical techniques, confirming successful incorporation of Ni into the Zn-BDC framework without compromising its structural integrity. The Ni(10)-Zn-BDC catalyst, in particular, exhibited remarkable efficiency in facilitating the reaction under mild conditions. Furthermore, the catalyst demonstrated excellent recyclability and stability, maintaining consistent catalytic performance over multiple cycles. These findings highlight Ni(x)-Zn-BDC as a promising and sustainable material for the synthesis of dihydropyrimidinones, underscoring its potential in green and efficient catalytic processes.