LAUSR

Abstract Two new bis(thiosemicarbazone) ligands 2-[1-(2-{3-[2-({2[(methyl)carbothioyl]hydrazono}-methyl)phenoxy]propoxy}phenyl)methylidene]-N 1 -(methyl)-1-hydrazinecarbothiamide ( H 2 L5 ), 2-[1-(2-{3-[2-({2-[(methyl)carbothioyl]hydrazono}methyl)phenoxy]-2-hydroxypropoxy}-phenyl)methylidene]-N 1 -(methyl)-1-hydrazinecarbothiamide ( H 3 L6 ), and their Cu(II) complexes were synthesized and characterized by physico-chemical and spectroscopic methods. Among eight DFT calculation methods PBE0/6-311+G(d,p)//B3LYP/6-31+G(d) method was the best method to predict one-electron reduction potentials ( E calc ) of these two new and four previously prepared copper complexes in DMF. The effects of solvation in DMF is incorporated as a self-consistent reaction field (SCRF) using the PCM solvent model. This model was capable to predict the experimental results with an error in the range of −0.200 to −0.002 V in comparison with experimental values ( E exp ) derived from CV. The changes in solvation energy, ΔΔ solv G °, play important role and without considering the effects of solvation in the calculations, the results are more different from the experimental ones. The calculated one-electron reduction potentials correlated with the energies of both the LUMO of the Cu II and the HOMO of the Cu I complexes.