Akademik Veri Yönetim Sistemi
JOURNAL OF MOLECULAR STRUCTURE, cilt.1361, 2026 (SCI-Expanded, Scopus)
In this study, three new 2-(2-alkoxyformylhydrazono)butan-3-one oxime ligands (L1-L3), containing both hydrazone and oxime functional groups, were synthesized by the condensation of diacetylmonoxime with methyl, ethyl, and tert-butyl carbazates, which are hydrazide compounds, respectively, and their corresponding Pd(II) complexes (C1-C3) were successfully obtained. The synthesized compounds were characterized by elemental analysis, FT-IR, UV-Vis, NMR, and ESI-MS techniques. Spectroscopic data indicated that the ligands coordinated to the Pd(II) center through the azomethine and oxime nitrogen atoms after deprotonation of the oxime group, forming square-planar complexes with a d8 electronic configuration. In addition, single-crystal Xray diffraction analyses of ligand L3 and complex C1 confirmed their molecular geometry. The DNA cleavage activity of the compounds was examined using pBR322 plasmid DNA, revealing that the Pd(II) complexes exhibited oxidative nuclease activity in the presence of H2O2. At the same time, C3 also displayed intrinsic activity in the absence of an activator. The optimized geometries of the ligands and their Pd(II) complexes were obtained using Density Functional Theory (DFT) calculations, which showed good agreement with experimental data and confirmed the square-planar coordination environment around the Pd(II) center. The donor-acceptor interactions within the compounds were investigated using NBO analysis to gain further insight into their electronic structures. In addition, MEP surface maps were calculated for the ligands and Pd(II) complexes to identify the most probable reactive sites. Frontier molecular orbital (FMO) and chemical reactivity analyses revealed that complexation with Pd(II) narrowed the HOMO-LUMO energy gap and increased softness, suggesting that the Pd(II) complexes may exhibit higher reactivity and electron-accepting ability compared with the free ligands. Molecular docking studies suggested that the Pd(II) complexes exhibited relatively higher binding affinity to B-DNA than the free ligands.