Quantum chemical studies and effect of gamma irradiation on the spectral, thermal, X‐ray diffraction and DNA interaction with Pd (II), Cu(I), and Cd (II) of hydrazone derivatives

• Published in: Applied organometallic chemistry Vol. 35; no. 4
• Main Authors: Aly, Samar A., Elganzory, Hussein H., Mahross, Mahmoud H., Abdalla, Ehab M.
• Format: Journal Article
• Language: English
• Published: Chichester Wiley Subscription Services, Inc 01-04-2021
• Subjects: Chemistry; complexes; Coordination compounds; Crystallites; Deoxyribonucleic acid; DFT; DNA; DNA interaction; Electronic spectra; Energy gap; Gamma irradiation; Hydrazones; Ligands; Mathematical analysis; Molecular orbitals; NMR; Nuclear magnetic resonance; Palladium; Quantum chemistry; Thermal stability; Thermodynamic properties; X-ray diffraction; XRD; γ‐irradiation
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.6153

A new series of Pd (II), Cd (II), and Cu(I) complexes with ((Z)‐2‐(phenylamino)‐N′‐(thiophen‐2‐ylmethylene)acetohydrazide)(H2LB) has been prepared. FT‐IR, 1H‐NMR, electronic spectra, Powder X‐ray, thermal behavior, theoretical methods and DNA interaction of ligand and of Pd (II) and Cu(I) complexes before and after γ‐irradiation are studied. The 1H NMR spectrum of the ligand after γ‐irradiation shows the signals appear at the same position or slightly shift, but the intensity of the bands after γ‐irradiation is higher than before irradiated. X‐ray diffraction (XRD) studies exhibited the samples in nanorange, the crystallite size is 1.94, 4.81 nm for both unirradiated (B1 and B3) and 2.93, 4.72 nm for irradiated (A1 and A3). The thermal stability of the complexes after γ‐irradiation increase than before γ‐irradiation. The possible structures of the metal complexes have been computed using the molecular mechanic calculations UFF using quantum chemical software by Gaussian 09 W program. The calculations are performed with DFT/B3LYP/LANL2DZ to obtain the optimized molecular geometry. Some important quantum chemical descriptors of the metal complexes were calculated such as HOMO, LUMO, and energy gap. Metal complexes before and after irradiation in the absence and presence of increasing amounts of CT‐DNA exhibit that the absorption intensities decrease with increasing the concentration of DNA.
Figure (1) Electronic absorption spectra of Pd complexes (A1 and B1) in the absence and presence of increasing amounts of CT‐DNA. Arrows show the changes in absorbance with respect to an increase in the DNA concentrationFigure (2) Molecular orbital for Pd complex using B3LYP method with LANL2DZ basis set.