The influence of ligand conformation on the thermal spin transitions in iron(III) saltrien complexes.

We report the syntheses of six new salts of the iron(III) complexes of four hexadentate Schiff bases of the saltrien-type derived from 1,8-diamino-3,6-diazaoctane and 2 equiv. of the appropriate salicylaldehyde derivative. Three of these new compounds undergo gradual spin-transitions centred between 155-204 K in the solid state, that proceed to 35-50% completeness. One of the other compounds remains high-spin on cooling, another is low-spin, while the last undergoes spin-crossover centred above room temperature. This spin-state variability is typical of solid compounds of this type. As an aid to understanding this behaviour, the crystal structures and magnetochemistry of the known spin-crossover salts [Fe(saltrien)]PF6, [Fe(saltrien)]ClO4 and [Fe(saltrien)]BPh4 have also been reexamined. The structural chemistry of all three salts was found to differ significantly from what has been previously reported. Correlation of the crystal structures and magnetic behaviour of the compounds in this and previous work suggests that the disposition of the two ligand phenoxy groups plays an important role in determining whether high-spin [Fe(saltrien)]+ complexes can undergo thermal spin-transitions.