FeII Spin crossover materials based on dissymmetrical N4 Schiff bases including 2-pyridyl and 2R-imidazol-4-yl rings: Synthesis, crystal structure and magnetic and Mössbauer properties

The synthesis and characterization of new symmetrical FeII complexes, [FeLA(NCS)2] (1), and [FeLBx(NCS)2] (2–4), are reported (LA is the tetradentate Schiff base N,N′-bis(1-pyridin-2-ylethylidene)-2,2-dimethylpropane-1,3-diamine, and LBx stands for the family of tetradentate Schiff bases N,N′-bis[(2-R-1H-imidazol-4-yl)methylene]-2,2-dimethylpropane-1,3-diamine, with: R = H for LB1 in 2, R = Me for LB2 in 3, and R = Ph for LB3 in 4). Single-crystal X-ray structures have been determined for 1 (low-spin state at 293 K), 2 (high-spin (HS) state at 200 K), and 3 (HS state at 180 K). These complexes remain in the same spin-state over the whole temperature range [80–400 K]. The dissymmetrical tetradentate Schiff base ligands LCx, N-[(2-R2-1H-imidazol-4-yl)methylene]-N′-(1-pyridin-2-ylethylidene)-2,2-R1-propane-1,3-diamine (R1 = H, Me; R2 = H, Me, Ph), containing both pyridine and imidazole rings were obtained as their [FeLCx(NCS)2] complexes, 5–10, through reaction of the isolated aminal type ligands 2-methyl-2-pyridin-2-ylhexahydropyrimidine (R1 = H, 5–7) or 2,5,5-trimethyl-2-pyridin-2-ylhexahydropyrimidine (R1 = Me, 8–10) with imidazole-4-carboxaldehyde (R2 = H: 5, 8), 2-methylimidazole-4-carboxaldehyde (R2 = Me: 6, 9), and 2-phenyl-imidazole-4-carboxaldehyde (R2 = Ph: 7, 10) in the presence of iron(II) thiocyanate. Together with the single-crystal X-ray structures of 7 and 9, variable-temperature magnetic susceptibility and Mössbauer studies of 5–10 showed that it is possible to tune the spin crossover properties in the [FeLCx(NCS)2] series by changing the 2-imidazole and/or C2-propylene susbtituent of LCx.

Single-crystal X-ray structures, variable-temperature magnetic susceptibility and Mössbauer studies show that it is possible to tune the spin crossover properties in the novel [FeLC(NCS)2] series by changing the 2-imidazole and/or C2-propylene susbtituent of the dissymmetrical tetradentate Schiff base ligands LC containing both pyridine and imidazole rings.Figure optionsDownload as PowerPoint slide