Spectroscopic, thermal analysis and DFT computational studies of salen-type Schiff base complexes

Abstract

A new series of metal(II) complexes of Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) have been synthesized from a salen-type Schiff base ligand derived from o-vanillin and 4-methyl-1,2-phenylenediamine and characterized by elemental analysis, spectral (IR, UV-Vis, (1)H NMR, (13)C NMR and EI-mass), molar conductance measurements and thermal analysis techniques. Coats-Redfern method has been utilized to calculate the kinetic and thermodynamic parameters of the metal complexes. The molecular geometry, Mulliken atomic charges of the studied compounds were investigated theoretically by performing density functional theory (DFT) to access reliable results to the experimental values. The theoretical (13)C chemical shift results of the studied compounds have been calculated at the B3LYP, PBEPBE and PW91PW91 methods and standard 6-311+G(d,p) basis set starting from optimized geometry. The comparison of the results indicates that B3LYP/6-311+G(d,p) yields good agreement with the observed chemical shifts. The measured low molar conductance values in DMF indicate that the metal complexes are non-electrolytes. The spectral and thermal analysis reveals that all complexes have octahedral geometry except Cu(II) complex which can attain the square planner arrangement. The presence of lattice and coordinated water molecules are indicated by thermograms of the complexes. The thermogravimetric (TG/DTG) analyses confirm high stability for all complexes followed by thermal decomposition in different steps.

Keywords: Coats–Redfern; Metal Schiff base complex; Octahedral geometry; Phenylenediamine; Salen-type Schiff base; Tetradentate ligand.