FeIII Quinolylsalicylaldimine Complexes: A Rare Mixed‐Spin‐State Complex and Abrupt Spin Crossover |
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| Authors: | Prof. Dr. David J. Harding Darunee Sertphon Prof. Dr. Phimphaka Harding Prof. Dr. Keith S. Murray Dr. Boujemaa Moubaraki Prof. Dr. John D. Cashion Harry Adams |
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| Affiliation: | 1. Molecular Technology Research Unit Cell, Walailak University, Thasala, Nakhon Si Thammarat, 80161 (Thailand), Fax: (+66)?75‐672004;2. School of Chemistry, Monash University, Melbourne, Victoria, 3800 (Australia);3. School of Physics, Monash University, Melbourne, Victoria, 3800 (Australia);4. Department of Chemistry, University of Sheffield, Sheffield, S3 7HF (UK) |
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| Abstract: | A new synthesis of (8‐quinolyl)‐5‐methoxysalicylaldimine (Hqsal‐5‐OMe) is reported and its crystal structure is presented. Two FeIII complexes, [Fe(qsal‐5‐OMe)2]Cl ? solvent (solvent=2 MeOH ? 0.5 H2O ( 1 ) and MeCN ? H2O ( 2 )) have been prepared and their structural, electronic and magnetic properties studied. [Fe(qsal‐5‐OMe)2] Cl ? 2 MeOH ? 0.5 H2O ( 1 ) exhibits rare crystallographically independent high‐spin and low‐spin FeIII centres at 150 K, whereas [Fe(qsal‐5‐OMe)2]Cl ? MeCN ? H2O ( 2 ) is low spin at 100 K. In both structures there are extensive π–π and C? H???π interactions. SQUID magnetometry of 2 reveals an unusual abrupt stepped‐spin crossover with T1/2=245 K and 275 K for steps 1 and 2, respectively, with a slight hysteresis of 5 K in the first step and a plateau of 15 K between the steps. In contrast, 1 is found to undergo an abrupt half‐spin crossover also with a hysteresis of 10 K. The two compounds are the first FeIII complexes of a substituted qsal ligand to exhibit abrupt spin crossover. These conclusions are supported by 57Fe Mössbauer spectroscopy. Both complexes exhibit reversible reduction to FeII at ?0.18 V and irreversible oxidation of the coordinated qsal‐5‐OMe ligand at +1.10 V. |
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| Keywords: | electrochemistry iron spin crossover supramolecular chemistry X‐ray diffraction |
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