Applied Organometallic Chemistry最新文献

Exposure to heavy metals, even at minimal levels, poses serious health risks to both humans and animals. Therefore, the demand for innovative and efficient sensing materials using advanced methodologies is rapidly increasing. In this research, a new series of naphthol-triazole linked organosilane (6MNT) was successfully synthesized via a Cu(I)-catalyzed click reaction and thoroughly characterized through FT-IR, ¹H and ¹³C NMR, and mass spectrometry. The UV–Visible and fluorescence spectroscopic analysis of 6MNT revealed its remarkable selectivity toward V (III) in the presence of other metal cations. Detection limits (LOD) of V (III) were measured as 2.9 × 10⁻⁷ M and 4.4 × 10⁻⁸ M using absorption and emission spectroscopy, respectively. DFT calculations performed via Gaussian 09 software provided insight into the binding interactions between 6MNT and V (III). The molecular docking and MD simulation studies indicated a strong binding affinity (−6.95 kcal/mol) and stable interactions of 6MNT with the active sites of vanadium apochloroperoxidase protein, highlighting its potential biological relevance.

A new two-dimensional (2D) lanthanide metal–organic framework [Eu₂(ATA)₃(phen)₂]_n (Eu-MOF, H₂ATA = 2-amino terephthalic acid, phen = 1,10-phenanthroline) was successfully self-assembled via a simple solvothermal method. Then D-camphoric acid (D-Cam) was grafted onto Eu-MOF by post-synthetic modification (PSM) through a mechanochemical approach, successfully fabricating the chiral material Eu-MOF-D-Cam. Remarkably, this modification not only significantly enhanced the luminescent properties but also introduced the chiral sites for enantioselective sensing of mandelic acid (MA) enantiomers. The enantioselectivity factor α (α = K_SV(R-MA)/K_SV(S-MA)) of Eu-MOF-D-Cam was 2.56. These findings establish Eu-MOF-D-Cam as a promising photoluminescent sensor for chiral discrimination of R/S-MA enantiomers.

A novel family of binuclear transition metal complexes was synthesized with M = Zinc (II), Cobalt (II), Nickel (II), Copper (II), and Manganese (II). These complexes, formulated as [M₂(L)Cl₂(H₂O)₆] and [M′₂(L)Cl₂(H₂O)₂], were prepared using (E)-2,4-dihydroxy-5-((3-hydroxyphenyl)diazenyl)benzoic acid (LH₂), a newly synthesized pentadentate/hexadentate azo dye ligand. Their coordination patterns and structural features were systematically investigated using a wide range of spectroscopic and analytical techniques, including Fourier Transform Infrared (FTIR) spectroscopy, UV–Vis spectroscopy, magnetic susceptibility measurements, elemental analysis, thermal studies (TGA/DTA), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) analysis. An octahedral geometry surrounding the metal centers was confirmed by magnetic and spectroscopic evidence. XRD patterns indicated a hexagonal structure for the ligand and a cubic structure for the Cobalt (II) complex, with nanocrystalline sizes of ~20–29 nm. The complexes' electronic structures, frontier molecular orbitals (HOMO–LUMO gap), molecular electrostatic potential (MEP), optical responses, and ideal geometries were all investigated using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) computations. Both metal-to-ligand (MLCT) and ligand-to-metal (LMCT) charge-transfer transitions were visible in the simulated TD-DFT spectra. While HOMO-LUMO gaps ranged from 1.76 to 3.12 eV, suggesting varied reactivity across complexes. ESR spectroscopy of the Copper (II) complex indicated strong metal–ligand covalency and confirmed a binuclear configuration. Biological screening showed enhanced antibacterial activity for all complexes, especially against Pseudomonas aeruginosa. Antioxidant studies revealed the Ni (II) complex as the most potent (IC₅₀ ≈ 26.9 μM). Cytotoxicity assays (SRB) on MCF-7 cells showed that the Ni (II) complex exhibited the highest activity (IC₅₀ = 6.33 μM), comparable to doxorubicin (5.15 μM), followed by LH₂ (22.97 μM) C,o (II) (44.28 μM), Zn (II) (59.41 μM), and Cu (II) (78.87 μM). Molecular docking with EGFR, HER2, and 1MBB confirmed strong binding, supported by QSAR and ADMET profiles suggesting drug-likeness and low toxicity. These results highlight their therapeutic and optoelectronic potential.

Herein, we report an effective catalytic methodology for the construction of α,β-unsaturated amides via acceptorless dehydrogenative coupling (ADC) of alcohols using newly synthesized binuclear ruthenium (II) complex [(η⁶-p-cymene)₂Ru₂Cl₂(μ-L)] (where L = N′-4-fluoro benzoyl-4-fluorobenzohydrazide) as catalyst. The structural characterization of the newly synthesized ruthenium complex has been established using analytical and various spectroscopic techniques (FT-IR, UV–vis, and NMR). Further, the molecular structure of the complex has been authenticated by a single-crystal X-ray diffraction method. The catalytic system displaces a wide range of α,β-unsaturated amides (16 examples), which have been obtained from the reaction of diverse primary alcohols and aryl amide with maximum of 93% of yield. The protocol for α-alkenylation of amide involves through C-C bond formation utilizing 0.5 mol% of catalyst loading with the release of release water and hydrogen gas as the only by-products. The control experiments evidence the initial dehydrogenation of alcohols into their corresponding aldehydes and C=C bond formation through aldol condensation. In addition, a large-scale synthesis of one of the amides (E)-3-(4-methoxyphenyl)-N-phenyl acrylamide has been performed with the yield of 78%, which proves the effectiveness of the present catalytic protocol.

The intratumoral microbiota plays a pivotal role in promoting cancer cells' proliferation and metastasis, and antibacterial agents exhibit significant efficacy in inhibiting cancer cells' migration. In this study, Zn-Cip was synthesized using Zn²⁺ and ciprofloxacin hydrochloride monohydrate as a ligand. Mn²⁺, which was known for its reactive oxygen species (ROS) generating capability, was incorporated into the Zn-Cip to construct the treatment system Mn-Zn-Cip. The material showed ideal antibacterial activity against Staphylococcus aureus and Escherichia coli, thereby effectively inhibiting cancer cells' migration. Meanwhile, Mn-Zn-Cip exhibited significant antitumor performances. This study emphasized the potential of Mn-Zn-Cip as an advanced platform for tumor treatment.

The fusion of benzene with selenophene motifs in hybrid configurations yields two distinct structural types: condensed benzo[b]selenophenes and benzo[c]selenophenes. Benzo[c]selenophenes are distinguished by the placement of a selenium atom at the second position rather than the first. To date, no specific studies have focused exclusively on this scaffold, which has been predominantly utilized as a versatile building block in various applications. The synthesis of benzo[c]selenophenes and their analogues can be accomplished through multiple chemical pathways, including (i) selenation reactions using reagents like Woollins' reagent, Na₂Se₂/DMSO, 1,1,1,3,3,3-hexabutyldistannaselenane in toluene, selenium/NMP, and Na₂Se in THF; (ii) Suzuki, Stille, and Sonogashira coupling reactions; (iii) photocyclization reactions; (iv) nucleophilic and metallic substitution reactions; (v) [2 + 2 + n] cycloaddition reactions; and (vi) organometallic reactions, among other methods.

This study focuses on the synthetic modification of satraplatin through axial position substitution by introducing the bioactive molecule cannabidiol (CBD) at the axial position, leading to novel multifunctional antitumor complexes S1–S5. The results demonstrate that the target complexes exhibit significantly optimized physicochemical properties with improved lipo–hydro partition coefficients, combining both lipophilic and hydrophilic characteristics that favor drug metabolism. Remarkably enhanced in vitro antitumor activity was observed: S3 showed 4.3-fold higher cytotoxicity than satraplatin in HCT-116 cells, with superior efficacy against drug-resistant cells. S5 demonstrated 22-fold greater antiproliferative activity than both parental satraplatin and CBD alone in A549 cells, likely attributable to its haloacetic axial group enhancing mitochondrial targeting for trifunctional synergistic antitumor effects. Mechanistic studies revealed that the complexes are reduced by ascorbic acid in vivo to release both CBD and Pt (II). CBD disrupts redox homeostasis through ROS accumulation and impairs mitochondrial membrane potential, synergizing with Pt (II)-induced DNA damage to promote cancer cell apoptosis. The introduction of bioactive moieties like CBD with excellent biological functions into the axial position of Pt (IV) complexes not only optimizes physicochemical properties but also enriches antitumor functionality. Compared with conventional platinum drugs, these complexes demonstrate significantly enhanced cytotoxicity (S3 is 9.5-fold more toxic than cisplatin in HCT-116 cells; S5 shows 33-fold higher antiproliferative activity in A549 cells) while maintaining superior activity against resistant cells through CBD-Pt (II) synergy. This study provides valuable insights for overcoming limitations of traditional platinum drugs and developing synergistic antitumor agents with enhanced efficacy.

Magnetic adsorption materials show great potential in wastewater treatment, but there are few relevant cases for the removal of crystalline violet (CV), while the removal of CV and heavy metal ions is even more of a challenge. In this experiment, Fe₃O₄ microspheres are used as the core and hydrothermally wrapped with stacked clusters of MnO₂ on the outside to increase the specific surface area of the composite. Finally, the Fe₃O₄@MnO₂ composite is wrapped with β-cyclodextrin (β-CD) by cross-linking grafting with the silane coupling agent KH-560, bringing a large number of O atoms and epoxy groups to the adsorbent. The prepared Fe₃O₄@MnO₂@β-CD composite has a large specific surface area of 209.897 m² g⁻¹ and has good removal of CV and Mn (VII). The effects of adsorbent type, initial concentration, temperature, and contact time on the adsorption performance were investigated. The results for the adsorption of CV and Mn (VII) show that the adsorption behavior follows a pseudo-second-order kinetic model and fits well with the Langmuir isotherm, indicating predominant monolayer adsorption, and the adsorption is governed by a combination of intraparticle and film diffusion mechanisms. Thermodynamic studies confirm its spontaneous and heat-absorbing nature. Remarkably, after five reuse cycles, there is minimal loss in removal rate. The prepared Fe₃O₄@MnO₂@β-CD composite is a green and renewable adsorbent, which has a wide application prospect in the adsorption field.

The development of bifunctional catalytic materials bearing Lewis acid and base activity sites toward the cycloaddition of CO₂ and epoxides to value-added cyclic carbonate under cocatalyst-free conditions is needed in particular. In this work, an imidazolium functionalized Zn (II)-porphyrin ZnTAEImP was first designed and synthesized. Subsequently, a series of porous organic polymers, named POP-ZnTAEImP/DVB(1:m) (m = 30, 50, 70), were prepared through the free-radical copolymerization of ZnTAEImP with divinylbenzene (DVB). The obtained POP-ZnTAEImP/DVB(1:m) exhibited a high specific surface area and good thermal stability. As bifunctional heterogeneous catalysts, POP-ZnTAEImP/DVB(1:m) showed excellent catalytic activities in CO₂ cycloaddition with epichlorohydrin under the condition of solvent-free. In particular, the POP-ZnTAEImP/DVB(1:50) demonstrated the highest catalytic activity (TON = 2880) and was applicable to a variety of epoxides. Furthermore, only a slight decrease in catalytic activity was observed after five cycles. Activation energy (E_a) for this reaction was determined to be 52.4 kJ/mol. This work provides a valuable strategy for designing efficient binary heterogeneous catalysts for the high-efficiency fixation of CO₂.