Physical Characteristic and Molecular Structure of Spin-Crossover Iron(III) Complexes of Monoclinic Form with Hexadentate Ligands Derived from Triethylenetetramine and Salicylaldehyde (Fe(sal2trien))BPh4acetone.

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Iron(III) complexes of [FeL]BPh4·acetone containing the hexadentate ligand derived from triethylenetetramine and salicylaldehyde have been synthesized. These complexes were grown in two crystalline forms, monoclinic and the twin crystals. The crystal structure of the monoclinic form was determined at 290 K, at which temperature the complex is in a transition spin-state between high- and low-spin states; the spin-state interconversion rate of the monoclinic form is as fast as the inverse of the Mössbauer lifetime (1×10−7s) above 200 K. The monoclinic crystal of [FeL]BPh4·acetone is of space group P21⁄a, with a=27.418(4), b=10.097(2), c=14.726(3) Å, β=98.00(1)°C, and Z=4. The average bond distances of Fe–O (1.875 Å), Fe–Nimine (1.988 Å), and Fe–Namine (2.069 Å) are in good agreement with the expected values for the transition spin-state between high- and low-spin states. Twin crystals are in a high-spin state over the temperature range 78–320 K.
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