Syntheses and magnetic properties of iron(III) complexes with imidazole groups

Iron(III) complexes with the general formula of [Fe (R-Himap)₂]X and [Fe(R-Himat)₂]X (Himap = shiff-base prepared from the condensation of 4-formylimidazole and 2-aminophenol, Himat = shiff base prepared from the condensation of 4-formylimidazole and 2-aminobenzenethiol, and R = H, Me, Ph; X = ClO₄, NO₃, BPh₄) have been synthesized. The complexes have an N₄O₂ donor set or an N₄S₂ donor set. These complexes have 5 and 5 member rings around an iron(III) atom per one chelate ring, that is, "5-5 member rings". The crystal structure, Mössbauer spectra, magnetic properties and absorption spectra of the complexes were examined. In addition, [Fe (Himsa)₂]ClO₄ having "5-6 member rings" of an N₄O₂ donor set and [Fe (Ph-Himap)(Ph-imap)] obtained by the deprotonation of [Fe (Ph-Himap)₂]ClO₄ have been also synthesized, and the Mössbauer spectra and magnetic properties of those complexes were examined. The X-ray structure of a single crystal of [Fe (Himap)₂]BPh₄ was determined: C₄₄H₃₆N₆BO₂Fe, triclinic, space group P(# 2), a = 12.452(2) Å, b = 12.748(2) Å, c = 11.996(2) Å, = 103.97(1)°, = 90.78(1)°, = 84.70(1)° and Z = 2. The moiety of an iron atom of [Fe(Himap)₂]BPh₄ was a pseudo octahedron with an FeN₄O₂ geometry. [Fe(R-Himap)₂]X was in high-spin state (about 5.9 B.M. at 80 K in solid state), and [Fe(R-Himat)₂]X was in low-spin state (about 2.0 B.M. at 293 K). The complex [Fe(Himsa)₂]ClO₄ with "5-6 member rings" and the deprotonated complex [Fe(Ph-Himap)(Ph-imap)] were in the high-spin state (6.0 B.M. at 80 K). It is concluded that the ligand field strength of an N₄S₂ donor set is stronger than that of an N₄O₂ donor set.