Abstract

A series of iron(iii) complexes [Fe(naphEen)<inf>2</inf>]X·sol (naphEen = 1-{[2-(ethylamino)-ethylimino]methyl}-2-naphtholate; X = F, sol = 0.5CH<inf>2</inf>Cl<inf>2</inf>·H<inf>2</inf>O 1; sol = H<inf>2</inf>O, X = Cl, 2 and X = Br 3) and [Fe(naphEen)<inf>2</inf>]I 4 has been prepared. The UV-Vis spectra reveal clear differences for 1 which DFT/TDDFT calculations suggest are due to an equilibrium between [Fe(naphEen)<inf>2</inf>]F and [Fe(naphEen)<inf>2</inf>F], the latter having a coordinated F ligand. The X-ray crystal structures of 2-4 show LS Fe(iii) centres in all cases and extensive aryl interactions that link the Fe centres into supramolecular squares. In 3 at room temperature the compound loses half an equivalent of water resulting in a change in space group from Monoclinic P2<inf>1</inf>/n to C2/c. Magnetic studies indicate that 1 is trapped in a mixed spin state being ca. 40% HS while 2-4 are effectively low spin up to 350 K. In contrast, Mössbauer spectroscopic studies of 1 indicate a gradual but incomplete spin crossover. The magnetic properties of 2-4 contrast with the related [Fe(salEen-X)<inf>2</inf>]anion derivatives which are often spin crossover active.