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Issue 35, 2018
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Solvatomorphism and anion effects in predominantly low spin iron(III) Schiff base complexes

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A series of iron(III) complexes [Fe(naphEen)2]X·sol (naphEen = 1-{[2-(ethylamino)-ethylimino]methyl}-2-naphtholate; X = F, sol = 0.5CH2Cl2·H2O 1; sol = H2O, X = Cl, 2 and X = Br 3) and [Fe(naphEen)2]I 4 has been prepared. The UV-Vis spectra reveal clear differences for 1 which DFT/TDDFT calculations suggest are due to an equilibrium between [Fe(naphEen)2]F and [Fe(naphEen)2F], the latter having a coordinated F ligand. The X-ray crystal structures of 2–4 show LS Fe(III) centres in all cases and extensive aryl interactions that link the Fe centres into supramolecular squares. In 3 at room temperature the compound loses half an equivalent of water resulting in a change in space group from Monoclinic P21/n to C2/c. Magnetic studies indicate that 1 is trapped in a mixed spin state being ca. 40% HS while 2–4 are effectively low spin up to 350 K. In contrast, Mössbauer spectroscopic studies of 1 indicate a gradual but incomplete spin crossover. The magnetic properties of 2–4 contrast with the related [Fe(salEen-X)2]anion derivatives which are often spin crossover active.

Graphical abstract: Solvatomorphism and anion effects in predominantly low spin iron(iii) Schiff base complexes

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Publication details

The article was received on 18 May 2018, accepted on 17 Aug 2018 and first published on 20 Aug 2018

Article type: Paper
DOI: 10.1039/C8DT02016G
Citation: Dalton Trans., 2018,47, 12449-12458

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    Solvatomorphism and anion effects in predominantly low spin iron(III) Schiff base complexes

    T. Boonprab, P. Harding, K. S. Murray, W. Phonsri, S. G. Telfer, A. Alkaş, R. Ketkaew, Y. Tantirungrotechai, G. N. L. Jameson and D. J. Harding, Dalton Trans., 2018, 47, 12449
    DOI: 10.1039/C8DT02016G

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