Five new nickel(II) complexes have been synthesised with an NNO donor tridentate aroylhydrazone (HFPB) employing the chloride, nitrate, acetate and perchlorate salts, and all the complexes were physiochemically characterized. Elemental analyses suggested a deprotonated iminolate form of the ligand in four of the complexes, however in one case (2), two aroylhydrazone moieties are binding to the metal centre in the neutral and anionic forms. The structure of the bisligated complex 5, characterized using X ray diffraction studies affirmed that the metal has a distorted octahedral N4O2 coordination environment, with each of the two ligands coordinating through the pyridine nitrogen, imino-hydrazone nitrogen and the deprotonated oxygen of the hydrazone moiety. In order to compare and study the elctronic interactions and stabilities of the metal complexes various quantum chemical parameters were calculated. Moreover, Hirshfeld surface analaysis was carried out for complex 5 in order to determine the intermolecular interactions. The biophysical attributes of the ligand and complex 5 have been investigated with CT DNA and experimental outcomes show that the Ni(II) complex exhibited higher binding propensity towards DNA as compared to ligand. Furthermore, in order to specifically understand the type of interactions of the meatal complexes with DNA molecular docking studies were carried out. In addition, the electronic and related reactivity behaviors of the ligand and five Ni(II) complexes were effectuated using B3LYP/6-31++g**/LANL2DZ level. As expected, the obtained results from NBO computations displayed that the resonance interactions (n→π* and π→π*) play a determinant role in evaluating the chemical attributes of the reported compounds.