Steric Trapping of the High Spin State in FeIII Quinolylsalicylaldimine Complexes
Darunee Sertphon A , David J. Harding A D , Phimphaka Harding A , Keith S. Murray B , Boujemaa Moubaraki B and Harry Adams C
+ Author Affiliations
- Author Affiliations
A Molecular Technology Research Unit, Walailak University, Thasala, Nakhon Si Thammarat, 80161, Thailand.
B School of Chemistry, Monash University, Melbourne, Vic. 3800, Australia.
C Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
D Corresponding author. Email: hdavid@wu.ac.th
Australian Journal of Chemistry 67(11) 1574-1580 https://doi.org/10.1071/CH14177
Submitted: 28 March 2014 Accepted: 28 April 2014 Published: 12 June 2014
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 100 K 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.
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