Synthesis, characterization, mechanochromism and photochromism of [Fe(dm4bt)3][FeCl4]2 and [Fe(dm4bt)3][FeBr4]2, along with the investigation of steric influence on spin state

Abstract

The complexes [Fe(dm4bt)₃][FeCl₄]₂ (1) and [Fe(dm4bt)₃][FeBr₄]₂ (2) were prepared from the reaction of 2,2′-dimethyl-4,4′-bithiazole (dm4bt) with FeCl₃·6H₂O and FeBr₃, respectively, in methanol. Both complexes were characterized by IR, UV-Vis and ¹H NMR spectroscopy and their structures were studied by single-crystal diffraction. The methylated bithiazole led to high spin Fe(II) centers in the octahedral cation part of complexes 1 and 2 with Fe–N distance of 2.220 Å, in spite of the low spin octahedral Fe(II) complexes with unsubstituted bithiazole ligands. Crystal structure determination of 2 was performed at 90, 120 and 298 K. Temperature reduction to 90 K resulted in a decrease in the Fe–N bond length to 2.206 Å which is still in the range of high spin Fe(II). Complex 1 shows a reversible mechanochromic effect from the crystalline phase to powder form from red to yellow; it also displays reversible photochromism from yellow to green in solution under sunlight. The magnetic behaviour of the complexes was also studied at 2–300 K. The temperature dependence of χ_mT curves for the two forms of 1, crystal and powder, demands some changes in their magnetic behavior, causing different colors i.e. red and yellow. At low temperatures, χ_mT decreases where the decrease starts at around 65 K for compound 1, and at around 100 K for compound 2, due to different counterions. The two complexes exhibit antiferromagnetism at around 4 K.