Applied Organometallic Chemistry最新文献

In this study, the properties of the electron transport layer (ETL) were improved by doping with zinc oxide (ZnO) nanoparticles (NPs) in a PFN solution. The organic solar cells (OSCs) were entirely fabricated and tested under regular atmospheric conditions by using active materials composed of fluorene (F) and diketopyrrolopyrrole (DPP) monomers called PFDPP-2 copolymer, combined with poly(3-hexylthiophene) (P3HT), and synthesized with 0.075% catalyst and PC₇₁BM in a fullerene ternary system. P3HT and PFDPP-2 polymers were synthesized by direct arylation polymerization. Additionally, a non-fullerene binary system based on (PBDB-T-2F [PM6]:BTP-4Cl [Y7]) was also analyzed. The solar devices based on this binary system, with ZnO NPs-doped in the ETL layer, adopted the structure glass/ITO/PEDOT:PSS/PM6:Y7/PFN:ZnO NPs/FM. Field's metal (FM) is a eutectic alloy used as a top electrode, deposited vacuum-free. In contrast, the ternary system was configured with glass/ITO/PEDOT:PSS/P3HT:PFDPP-2:PC₇₁BM/PFN:ZnO NPs/FM. In the ternary system, a 39.9% improvement in current density (J_sc) was observed upon doping with ZnO NPs, achieving a maximum power conversion efficiency (PCE) of 4.02%, 5.5% more with respect to the ternary reference and 24.8% considering only P3HT in the active layer. A similar behavior was observed in binary solar cells, resulting in a 51.8% increase in J_sc compared to the reference cell without ZnO NPs. For the non-fullerene OSCs, the maximum PCE of 11.84% was achieved, representing a 2.7% improvement compared to the reference binary system without ZnO NPs. Regarding stability, both systems (binary and ternary) maintained their transmission bands partially during the first 200 h of operation, indicating a significant improvement in the stability of both devices. However, in P3HT:PFDPP-2:PC₇₁BM cells, PCE decreased by 11% after 400 h, whereas in PM6:Y7 cells, stability improved by 5% under the same conditions.

The development of efficient and selective chemosensors for detection of ions is vital owing to their environmental and biological significance. Among these cations, Fe³⁺ plays crucial role in physiological processes but also poses toxicity risks above threshold levels. The traditional analytical tools require complex instrumentation and there is prompt need for simple and colorimetric alternatives. CuAAC reaction hands us with powerful strategy for synthesizing a novel Sudan IV–based 1,2,3-triazole derivative for its selective colorimetric response to Fe³⁺, that can find practical applications. This research investigates use of “Sudan IV–based triazole chemosensor (ST)” via the “CuAAC” click reaction for selective colorimetric sensing of Fe³⁺ ions. The developed chemosensor ST was successfully characterized by FTIR, NMR (¹H,¹³C) and mass spectrometry. The UV–vis investigation of ST was conducted in “CH₃CN:H₂O, 4:1 v/v,” solvent medium using 0.20 mM solution of heterocyclic compound ST and 0.50 mM solutions of various metals such as Na⁺, K⁺, Ba²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, and Hg²⁺ were tested, with notable change using Fe³⁺ ions. The molecule ST exhibited LoD of 6.50 μM with negligible effect of interferent ions on selectivity and sensitivity. The Job's plot illustrated 1:1 stoichiometric ratio between the ST:Fe³⁺ complex. DFT simulations were performed using B3LYP/6/311G++(d,p) for ST and B3LYP/LANL2DZ for metal complex to investigate binding interactions. The reversible nature of the ST marks its importance to have potential to act as chemosensor multiple times without being degraded. The integrated experimental and theoretical results prove to be reliable for the detection of Fe³⁺ with potential applications in environmental monitoring, analytical chemistry, as well as biochemical applications.

A regioselective rhodium-catalyzed NH-indole-directed C–H coupling of 2-arylindoles with methyleneoxetanones, followed by TsCl/DMAP-mediated intramolecular amidation leading to biologically relevant benzo[3,4]azepino[1,2-a]indoles bearing a fused seven-membered ring is presented. Excellent functional group tolerance is demonstrated, yielding diverse indole-fused seven-membered-ring architectures and providing gramme quantities of products through scalability.

A novel silane–grafted Schiff base derivative, designated as compound 3, was synthesized and thoroughly characterized using ¹H NMR, ¹³C NMR, FT-IR, and mass spectrometry. The formation of its Ni(II) complex was confirmed by FT-IR, mass spectrometry, and DFT calculations. Photophysical studies revealed that compound 3 exhibits excellent selectivity and sensitivity toward Ni(II) ions, with low detection limits of 2.6 × 10⁻⁸ M (UV–Vis) and 3.0 × 10⁻¹⁰ M (fluorescence). DFT analysis supported the experimental findings, indicating the formation of a stable and energetically favorable complex. The compound also showed high accuracy in detecting Ni(II) in real water samples and exhibited low cytotoxicity toward HeLa cells, suggesting potential applications in both environmental monitoring and biological sensing. Overall, compound 3 functions as a stable, sensitive, and multifunctional fluorescent probe for Ni(II) ion detection.

Converting benzyl alcohol into benzaldehyde and hydrogen through photocatalytic oxidation is an effective approach to produce high-value-added chemicals and green energy. Hence, we adopted a physical method to synthesize a dual-functional Ni₃(PW₁₂O₄₀)₂/CdS S-scheme photocatalyst and verified that Ni₃(PW₁₂O₄₀)₂ can enhance the efficiency of CdS for benzyl alcohol valorization and hydrogen evolution. This optimized Ni₃(PW₁₂O₄₀)₂/CdS-20 composite displayed hydrogen production rate and benzaldehyde generation rate of 4.42 and 3.66 mmol·g⁻¹·h⁻¹, which are 7.6- and 11.4-fold higher than those of pristine CdS. In addition, the S-scheme charge transfer mechanism was proved through some experimental characterizations. The results indicate that the S-scheme heterojunction constructed from this composite material can efficiently facilitate the separation and migration of photogenerated carriers, thereby increasing the photocatalytic ability. This study provides a promising reference for incorporating polyoxometalates into metal sulfides to achieve efficient photocatalytic redox reactions.

A mononuclear Cu(II)–Schiff base complex, indicated as MBMBC, has been synthesized from a methoxyhydrazide-based ligand (HL), (E)-N′-(5-bromo-2-hydroxy-3-methoxybenzylidene)-4-methoxybenzohydrazide. The structure of the complex was determined by single-crystal X-ray diffraction analysis, which revealed that the Cu(II) centre is chelated by two oxygen and one imine nitrogen atom of the deprotonated ligand, an aquo and a nitrate ion to form a distorted square pyramidal geometry around the metal. The catalytic activity of the MBMBC complex was assessed for peroxidase-like oxidation reactions involving o-phenylenediamine (OPD), 3,3′-diaminobenzidine (DAB) and pyrogallol in methanol, using hydrogen peroxide (H₂O₂) as the oxidant. The complex also showed strong binding affinity towards calf thymus DNA (CT-DNA) and bovine serum albumin (BSA), as confirmed by UV–vis absorption spectroscopy. Significant fluorescence quenching of both the DNA–ethidium bromide (EB) complex and BSA was observed upon addition of the complex MBMBC, suggesting effective binding interactions. To support the experimental findings, molecular docking studies were performed to determine the binding site and interaction energies. Furthermore, the anticancer potential of the MBMBC complex was assessed on the cervical cancer cell line (HeLa) via an in vitro MTT assay, demonstrating its promising cytotoxic activity. Flow cytometry analysis using Annexin V/PI was performed to determine the mode of cell death, which was again reinforced by Hoechst 33342 staining. Generation of reactive oxygen species (ROS) was also envisaged using DCFH-DA. All these data together suggested that the complex MBMBC is demonstrating a potential anticancer effect.

The transition-metal-catalyzed borrowing hydrogen reaction has emerged as a powerful strategy for constructing chemical bonds, owing to its environmental friendliness and high reaction efficiency. In this study, we have synthesized and characterized two novel cobalt complexes (Co-1 and Co-2) bearing new bidentate ligands derived from thiomorpholine and 8-bromomethylquinoline. X-ray diffraction analysis reveals that the central cobalt atom in Co-2 is tetra-coordinated by one oxygen atom from the thiomorpholine N-oxide moiety and one nitrogen atom from the quinoline ring of ligand (L²), along with two chlorine atoms, adopting a regular tetrahedral geometry. The catalytic performance of these cobalt complexes is evaluated in the N-alkylation of amines with alcohols via a borrowing hydrogen strategy and Co-2 exhibits high catalytic activity. Importantly, the aromatic amines and primary alcohols containing different functional groups can be tolerated under present catalytic system. This work provides valuable insights into catalyst design and deepens our mechanistic understanding of this environmentally friendly reaction pathway.

In this work, a set of Pyridine Infused Schiff bases 3(a-b) has been synthesised and characterised using mass spectrometry, ¹³C NMR and ¹H NMR spectroscopy. Exploiting the X-ray crystallography, synthesised molecules 3a and 3b have been investigated. Compound 3a demonstrated remarkable sensitivity and selectivity towards Zn²⁺ ions, with minimal interference from other metals ions, as validated by UV–Vis and fluorescence spectroscopy. According to the job's plot, compound 3a links to Zn²⁺ in a 1:1 ratio. Through the analysis of Stern–Volmer plot and B-H plot, the binding constants were determined to be 8.17 × 10⁸ M⁻¹ and 5.70 × 10⁴ M⁻¹, and the Limit of detection (LOD) values were 0.035 nm and 5.912 μM, correspondingly. The synthesised compounds 3(a-b) were subjected to in vitro testing to assess their antibacterial activity against bacteria such as B. subtilis, S. aureus and Pseudomonas yielding positive findings. Additionally, the in vitro anticancer investigation was carried out, and impact of 3a was examined. Furthermore, compound 3a was docked to the cervical cancer protein, B. subtilis, S. aureus, and Pseudomonas, exhibiting encouraging binding energies of −8.33, −8.56, −9.82, and −8.65 Kcal/mol, respectively. The insights from both docking assessments as well as in vitro evaluations propose that compound 3a holds a great deal of promise as an antibacterial and anticancer drug. Additionally, 3a was effective in detecting Zn²⁺ ions in both real-world and pharmaceutical samples.

A palladium-catalyzed β-carbonyl alkylation of α-imino esters with readily available allylic/propargyl alcohols has been developed, enabling efficient synthesis of structurally diverse δ-carbonyl-α-amino acid esters and carbonyl-containing pyrrolidine derivatives. Mechanistic studies indicate that the reaction proceeds via a dehydrogenation-Michael addition or [3 + 2] cyclization pathway. This method offers an atom-economical and operationally straightforward strategy for the synthesis of highly functionalized Δ(1)-pyrrolines and pyrrolidines.

In this paper, a novel synthetic route is presented for the production of 99.99% high-purity anhydrous rare earth fluoride. First, organic system was used to produce high-purity diphenylpropanedione salt with hydrated rare earth salt as raw material through complex reaction, followed by recrystallization, and high-temperature vacuum drying to remove water of crystallization. Then, the resulting complex salt was reacted with ammonium hydride fluoride to prepare high-purity anhydrous rare earth fluoride. This method avoids the challenges associated with traditional dry methods, such as harsh reaction conditions and the easy introduction of impurities, as well as the high oxygen content and filtration difficulties of wet methods. The purity, oxygen content, and composition of the prepared rare earth fluoride products were analyzed using thermal analyzers, scanning electron microscopy, X-ray diffraction, inductively coupled plasma mass spectrometry, and an oxygen analyzer. The results demonstrated that this method produces rare earth fluoride with high purity, anhydrous properties, low oxygen content, and excellent crystallinity. This approach represents a green, efficient, and innovative preparation method for rare earth fluoride and offers a new pathway for the production of high-purity rare earth fluoride compounds.