Co(II), Ni(II), and Zn(II) complexes based on new hybrid imine-pyrazole ligands: structural, spectroscopic, and electronic properties

The present work reports the theoretical investigation of Co(II), Ni(II), and Zn(II) complexes containing Schiff bases (used as ligands) derived from the reaction of 2-hydroxy-l-naphthaldehyde with N-(2-aminoethyl) pyrazoles. The spectral analyses were carried out using infrared, Raman, and UV-Vis spectroscopy. Vibrational analyses were performed in order to investigate the mechanisms involving metal-ligand and intra-ligand vibrations and indicated the possibility of charge transfer related to the transitions n -> pi* and pi -> pi*. Structure optimizations and normal coordinate force field calculations were performed via the density functional theory (DFT) method at the HSE06/6-311G(d,p)/LanL2DZ level. A thorough analysis was also conducted regarding the nonlinear optical (NLO) properties and the natural bond orbital (NBO) of the complexes. The results show that these complexes have prospective application as materials for NLO. Furthermore, the NBO analysis confirms the coordination between the lone pair (LP) electrons of the donor atoms (O and N) and the metal acceptors. Finally, studies were conducted regarding the electronic properties of the complexes; among the properties investigated included the frontier molecular orbitals (FMO) and the molecular electrostatic potential (MEP), allowing to determine the energy gap and charge distribution.