SCHEDULED MAINTENANCE
Solvatomorphism and anion effects in predominantly low spin iron(iii) Schiff base complexes†
a
Keith S.
Murray,
b
Wasinee
Phonsri,
b
Shane G.
Telfer,
c
Guy N. L.
Jameson
e
and
David J.
Harding
*a
Abstract
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.
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