Investigations on the Spin States of Two Mononuclear Iron(II) Complexes Based on N-Donor Tridentate Schiff Base Ligands Derived from Pyridine-2,6-Dicarboxaldehyde

Abstract

Iron(II)-Schiff base complexes are a well-studied class of spin-crossover (SCO) activespecies 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 ligandfield. We have synthesized two mononuclear FeII 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 from2,6-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 theoreticallyand experimentally), single-crystal diffraction and magnetic susceptibility studies. The structural,spectroscopic and magnetic investigations revealed that 1 and 2 are with Fe–N6 distorted octahedralcoordination geometry and remain locked in LS state throughout the measured temperature rangefrom 5–350 K.