Steric trapping of the high spin state in FeIII quinolylsalicylaldimine complexes

Abstract

A new sterically bulky Schiff base ligand, N-(8-quinolyl)-5-tert-butylsalicylaldimine (Hqsal-5-tBu) has been prepared and a series of FeIII complexes, [Fe(qsal-5-tBu)2]Y (Y = Cl 1, ClO4 2, NO3 3, BF4 4) utilising this ligand are reported and fully characterised. UV-vis spectroscopic and electrochemical studies indicate that 1-4 are high spin (HS) in solution at room temperature and further suggest that the tBu group only slightly alters the electronic properties of 1-4 compared with related [Fe(qsal-5-X)2]+ systems. The structures of [Fe(qsal-5-tBu)2]Cl·4MeOH·H2O 1, [Fe(qsal-5-tBu)2]ClO4·MeOH 2, and [Fe(qsal-5-tBu)2]NO3 3 determined at 100K reveal HS FeIII centres in all cases. Four-fold parallel aryl embraces and π-π interactions serve to link the cations forming 2D sheets mirroring the motifs found in other [Fe(qsal-5-X)2]+ complexes. Despite this the tBu group causes strong distortions at the Fe centre which as magnetic studies reveal prevent spin crossover trapping 1-4 in the HS state.