Synthesis, characterization, electrochemical and spectroscopic investigation of cobalt(III) Schiff base complexes with axial amine ligands: The layered crystal structure of [CoIII(salophen)(4-picoline)2]ClO4 · CH2Cl2

Cobalt(III) complexes with potentially tetradentate salophen (H2salophen = N,N′–bis(salicylidene)-1,2-phenylenediamine) as equatorial ligand and with different axial amine ligands (NH3, cyclohexylamine, aniline, 4-picoline and pyridine) were synthesized and characterized by IR, 1H NMR, elemental analysis. Electronic spectra and electrochemical properties of the complexes were studied in DMF solutions. The lowest energy transitions, which occur between 464.8 and 477 nm, are attributed mainly to the intraligand charge transfer, confirmed by Zindo/S electronic structure calculations. The reduction potentials of Co(III)/Co(II) are more affected than those of Co(II)/Co(I) by the axial amine ligands. The crystal structure of the [CoIII(salophen)(4- picoline)2]ClO4 · CH2Cl2 was determined, indicating that the cobalt(III) center is six coordinated surrounded by the tetradentate salophen ligand and two 4-picoline ligands. The crystal packing of the complex shows a layered structure, in which the perchlorate counter ions and also the lattice solvent molecules are intercalated between the bc planes of the complex cations.