Green synthesis for new Co(II), Ni(II), Cu(II) and Cd(II) hydrazone-based complexes; characterization, biological activity and electrical conductance of nano-sized copper sulphate

Abstract

A series of new hydrazone complexes were prepared and perfectly elucidated to be 1:1 molar ratio with Cd(II) complex, while 1:2 (M:L) with Co(II), Ni(II) and Cu(II) complexes. The bidentate form of bonding was proposed for all complexes, either in octahedral or square-planer geometry with the Ni(II) complex. The UV-Vis spectral data as well as the magnetism of complexes (except Cd(II) one) suggested the geometry of complexes around the central atoms as well as the ligand field parameters (10Dq, B & β). In addition, the spin Hamiltonian parameters attribute to S = 1/2 and I = 3/2, were calculated for Cu(II) complex according to its ESR spectrum. XRD and SEM analyses were performed for selected complexes and the particle size of Ni(II) complex appeared in nan-scale. The DFT approach was used to optimize the ligand and its complexes under valence double-zeta polarized basis set and the correlation-consistent basis set. The ligand exhibited favorable characteristic for O(11) and O(12) atoms as orientation, nucleophilicity and charges, which help their priority in coordination. Genotoxicity of H2PHNH ligand and its Cd(II), Cu(II), and Ni(II) complexes degraded ctDNA into two distinct bands. Conductometric analysis for copper sulfate was performed in its bulk or nano-sized as well as in absence or presence of H2PHNH ligand. Using Fuoss-Hsia-Fernández-Prini (FHFP) equation, the molar conductance (Λm), the limiting molar conductance (Λo), Onsager slope (S), Walden product (Λo ηo), ion-pair interaction constant (KA), degree of dissociation (α), and activity coefficient (γ±) were calculated. The obtained data were elaborately discriminated according to the state of CuSO4 used (bulk & nano-sized) also in absence or presence of the ligand. Moreover, the thermodynamic parameters as well as the molar ratio of the formed complexes, were estimated in all systems studied. Finally, in bulk or nano-sized CuSO4 in presence of H2PHNH complexes, the formation constants and Gibbs free energies obey this order: Kf(1:2) > Kf (1:1) [M:L].