Cationic iron(III) complexes of the type [FeLⁿ(H₂O)₂]NO₃ (n=1 or 2) were accessed from the interaction of Fe(NO₃)₃·9H₂O with [N₂O₂] donor Schiff base (L) in 1:1 molar ratio. The Schiff base ligands were prepared from condensation of 2-hydroxy-1-naphthaldehyde with o-phenylenediamine or ethylenediamine in 2:1 molar ratio. Reaction of the aquated complexes with neutral N-donor molecules (X) viz. imidazole, benzimidazole and pyridine led to substitution of weakly held axial aquo groups affording new mixed ligand complexes, [FeLⁿX₂]NO₃. The compounds were characterized by elemental analyses, FT-IR, UV–Vis, solution electrical conductivity, FAB mass, ¹H and ¹³C NMR (ligands only) spectroscopy. The thermal study provided unambiguous evidence for the occurrence of coordinated water in the complexes. Room temperature magnetic susceptibility measurements are consistent with high spin octahedral iron(III) complexes. Cyclic voltammetry revealed a quasi-reversible one electron redox response (ΔE_p>100mV) assignable to Fe(III)/Fe(II) couple with negative half wave potential. The ground state geometries of the aquo complex, [FeL²(H₂O)₂]NO₃ and pyridine complex, [FeL²(Py)₂]NO₃ were ascertained by density functional theory using dmol3 program with BLYP functional.