Spectroscopic, structural and theoretical studies of copper(II) complexes of tridentate NOS Schiff bases

• Copper(II) complexes of NOS Schiff bases were synthesized and characterized.
• Crystal structures of copper(II) complexes presented distorted octahedral geometry.
• Complexes are monomeric with no copper-to-copper interaction.
• DFT calculations were made at B3LYP level of 6-311G(d) basis set.
• The bromo-substituted complex indicated higher polarizability and reactivity.

Two newly synthesized Schiff bases (L4 and L5) were derived from the condensation reaction of 2-(methylthiomethyl)anilines and 4-methoxysalicylaldehyde. Coordination complexes of these and four previously reported NOS Schiff bases, Cu(L1)2–Cu(L6)2, were synthesized via the reflux reaction of the various Schiff base ligands with CuCl2·2H2O. The compounds were characterized by means of elemental analysis, FTIR and UV–Vis. The crystal structures of Cu(L1)2 and Cu(L2)2 were obtained by X-ray diffraction. The Schiff bases were coordinated to copper ion as monobasic tridentate ligands through the phenolic oxygen, azomethine nitrogen and thioether sulfur. The microanalyses of the coordination complexes were agreeable with bimolar binding of the ligands to the copper metal ion. The crystal structures of the copper complexes confirmed an octahedral geometry around the metal centre and showed they are mononuclear. The magnetic moment values indicated the presence of a lone electron in each copper(II) orbital and confirmed the mononuclearity of the complexes. The electronic spectra of the coordination compounds consist of the intraligand, charge transfer and d→d bands. Molecular modeling studies on the complexes (Cu(L1)2–Cu(L6)2) by employing DFT revealed that complex Cu(L5)2 possessed the smallest optimization energy as well as a small HOMO−LUMO energy gap which may best explain its higher polarizability as well as reactivity in comparison to the other complexes.

The crystal structure, HOMO (I) and LUMO (II) of Cu(L1)2.Figure optionsDownload as PowerPoint slide