Abstract
Structural and magnetic data on two iron (III) complexes with a hexadentate Schiff base chelating ligand and Cl− or BPh4− counterions are reported. In the solid state, the Cl− complex [Fe(5F-sal2333)]Cl, 1, is high spin between 5–300 K while the BPh4− analogue [Fe(5F-sal2333)]BPh4, 2, is low spin between 5–250 K, with onset of a gradual and incomplete spin crossover on warming to room temperature. Structural investigation reveals different orientations of the hydrogen atoms on the secondary amine donors in the two salts of the [Fe(5F-sal2333)]+ cation: high spin complex [Fe(5F-sal2333)]Cl, 1, crystallizes with non-meso orientations while the spin crossover complex [Fe(5F-sal2333)]BPh4, 2, crystallizes with a combination of meso and non-meso orientations disordered over one crystallographic site. Variable temperature electronic absorption spectroscopy of methanolic solutions of 1 and 2 suggests that both are capable of spin state switching in the solution.
Highlights
Spin crossover complexes (SCO) constitute an interesting class of materials exhibiting interconversion between different electronic states by varying temperature or pressure or by light.Many potential applications have been suggested for their use, including their utilization in data storage, sensors, and display technologies
We have studied the effect of ligand flexibility on spin state choices in both Fe(III) and Mn(III) using some of the families of hexadentate Schiff base ligands of the type shown in Figure 1 [1,2,3,4,5,6]
Such chelates are formed by a condensation reaction of linear tetra-amines and substituted salicylaldehydes, and our studies to date have focused mostly on complexes from the “222”, “323”, and “232” series, where the numbers indicate the number of methylene groups connecting adjacent nitrogen atoms
Summary
Spin crossover complexes (SCO) constitute an interesting class of materials exhibiting interconversion between different electronic states by varying temperature or pressure or by light.Many potential applications have been suggested for their use, including their utilization in data storage, sensors, and display technologies. We have studied the effect of ligand flexibility on spin state choices in both Fe(III) and Mn(III) using some of the families of hexadentate Schiff base ligands of the type shown in Figure 1 [1,2,3,4,5,6]. Such chelates are formed by a condensation reaction of linear tetra-amines and substituted salicylaldehydes, and our studies to date have focused mostly on complexes from the “222”, “323”, and “232” series, where the numbers indicate the number of methylene groups connecting adjacent nitrogen atoms.
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