Synthesis, spectroscopic (electronic, IR, NMR and ESR) and theoretical studies of transition metal complexes with some unsymmetrical Schiff bases

• Metal complexes of unsymmetrical Schiff bases have been prepared and characterized.
• Spectral studies of complexes show variations in bonding mode and stereochemistry.
• ESR shows axial interaction of solvent molecules in a square planar Cu(II) complex.
• DFT is used to correlate experimental and calculated data of the Ni(II) complexes.
• TDDFT interprets M → L charge transfer and d–d transitions high and low energy bands.

Two unsymmetrical Schiff bases, glyoxal salicylaldehyde oxalic acid dihydrazone (gsodh) and glyoxal salicylaldehyde malonic acid dihydrazone (gsmdh) and their Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The structures of metal complexes are elucidated on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, electronic, ESR, IR and NMR (1H and 13C) spectral studies. Both ligands show monobasic tetra-dentate behaviour, bonding through CO, two CN and a phenolate group. The electronic spectral studies in solid state indicate a square planar geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complexes. However, Co(II) and Cu(II) complexes adopt octahedral geometry in DMSO solution. The ESR spectra of Cu(II) complexes in DMSO solution at 77 K predict an elongated tetragonal distorted octahedral geometry around metal ion and presence of unpaired electron in dx2-y2dx2-y2 orbital. Further, the structures of ligands and their Ni(II) complexes have been satisfactorily modelled by calculations based on density functional theory (DFT). The electronic spectra of Ni(II) complexes are also analyzed in depth with the help of time dependent-DFT (TD-DFT). The theoretical analyses of electronic structure and molecular orbitals have demonstrated that the high-energy absorption bands are M → L charge transfer and low energy transitions are d–d transitions.

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