Abrupt spin crossover in iron(iii) complexes with aromatic anions.

Abstract

Two iron(iii) spin crossover complexes, [Fe(qsal-X)2]OTs·nH2O, (Br 1·H2O; I, 2·2H2O or non-solvated 1, 2) have been prepared and fully characterized. Structural studies of 1·H2O and 2·2H2O reveal the presence of 1D π-π chains linking the Fe(iii) centres and a strong XO halogen bond. In both complexes the 1D π-π chains are angled relative to each other, enforced by C-HX interactions. Magnetic studies reveal abrupt spin crossover in 1 (T1/2↓ = 258 K and T1/2↑ = 260 K) and 2 (T1/2 = 298 K) with T1/2 increasing on going from Br to I. The presence of abrupt spin crossover in both complexes shows that aromatic anions can be effective in the design of cooperative spin crossover systems.