Electrocatalytic reduction of carbon dioxide induced by bis(N-R-2-hydroxy-1-naphthaldiminato)-copper(II) (R = n-octyl, n-dodecyl): Magnetic and theoretical studies and the X-ray structure of bis(N-n-octyl-2-hydroxy-1-naphthaldiminato)-copper(II)

Copper(II) complexes of n-alkyl-2-hydroxy-1-naphthaldimine Schiff bases (with n-alkyl: n-octyl, and n-dodecyl) have been synthesized, to study steric and electronic effects of long alkyl chain substituents on their structure and properties. These complexes have been characterized with FT-IR, UV-Vis, magnetic susceptibility and cyclic voltammetry both in nitrogen and carbon dioxide atmosphere. Metal-ligand coordination is inferred from the shifting of the ν_CN stretching vibration mode in the 1610-1620 cm⁻¹ region when compared to that of the free ligand. The UV-Vis spectra show one band around 640 nm typical for square planar Cu(II) complexes. Results obtained from cyclic voltammetry indicate electrocatalytic reduction of carbon dioxide around −0.90 V (versus Ag/AgCl). Bis(N-n-octyl-2-hydroxy-1-naphthaldiminato)-copper(II) has been studied with X-ray diffraction. The molecular structure shows the copper atom in a planar environment and the n-octyl chains having thermal disorder. The crystal packing shows stacked units intermolecularly separated by 3.33 Å, probably due to π-π interactions between naphthyl groups, and Cu-O and O-O separations of 3.95 and 3.42 Å, respectively. The magnetic susceptibility data between 10 and 300 K are indicative of diluted paramagnetic behavior. Density functional theory calculations of spin density for the n-octyl complex shows the unpaired electron localized along the planar CuO₂N₂ moiety. The calculated electrostatic potential show electron rich regions on the oxygen atoms.