Iron(II)-Schiff base complexes are a well-studied class of spin-crossover (SCO) active species due to their ability to interconvert between a paramagnetic high spin-state (HS, S = 2, ⁵T₂) and a diamagnetic low spin-state (LS, S = 0, ¹A₁) by external stimuli under an appropriate ligand field. We have synthesized two mononuclear Fe^II complexes, viz., [Fe(L¹)₂](ClO₄)₂.CH₃OH (1) and [Fe(L²)₂](ClO₄)₂.2CH₃CN (2), from two N₆–coordinating tridentate Schiff bases derived from 2,6-bis[(benzylimino)methyl]pyridine. The complexes have been characterized by elemental analysis, electrospray ionization–mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR), solution state nuclear magnetic resonance spectroscopy, ¹H and ¹³C NMR (both theoretically and experimentally), single-crystal diffraction and magnetic susceptibility studies. The structural, spectroscopic and magnetic investigations revealed that 1 and 2 are with Fe–N₆ distorted octahedral coordination geometry and remain locked in LS state throughout the measured temperature range from 5–350 K.