Halogen Substituent Effect on the Spin-Transition Temperature in Spin-Crossover Fe(III) Compounds Bearing Salicylaldehyde 2-Pyridyl Hydrazone-Type Ligands and Dicarboxylic Acids

Four Fe(III) spin-crossover (SCO) compounds, [Fe(HL1)(2)](HCl(4)TPA) (1-Cl), [Fe(HL1)(2)](HBr(4)TPA) (1-Br), [Fe(HL2)(2)](HCl(4)TPA) (2-Cl), and [Fe(HL2)(2)](HBr(4)TPA) (2-Br) (HL1 = 4-chloro-2-nitro-6-(1-(2-(pyridine-2-yl)hydrazono)ethyl)phenolate; HL2 = 4-bromo-2-nitro-6-(1-(2-(pyridine-2-yl)hydrazono)ethyl)phenolate; HCl(4)TPA = 2,3,5,6-tetrachloro-4-carboxybenzoate; and HBr(4)TPA = 2,3,5,6-tetrabromo-4-carboxybenzoate), were synthesized to investigate the halogen substituent change effect in salicylaldehyde 2-pyridyl hydrazone-type ligands and dicarboxylic acids in SCO complexes to the spin-transition temperature. Crystal structure analyses showed that these compounds were isostructural. In addition, a one-dimensional hydrogen-bonded column was formed by the dicarboxylic acid anion and weak hydrogen bonds between the Fe(III) complexes. From Mossbauer spectroscopy and magnetic property measurements, these compounds were confirmed to exhibit gradual SCO. The spin-transition temperature can be shifted by changing the halogen substituent in the salicylaldehyde 2-pyridyl hydrazone-type ligands and dicarboxylic acids without changing the molecular arrangement in the crystal packing.