Solvatomorphism and anion effects in predominantly low spin iron(iii) Schiff base complexes. Issue 35 (22nd August 2018)

• Record Type: Journal Article
• Authors: Boonprab, Theerapoom; Harding, Phimphaka; Murray, Keith S.; Phonsri, Wasinee; Telfer, Shane G.; Alkaş, Adil; Ketkaew, Rangsiman; Tantirungrotechai, Yuthana; Jameson, Guy N. L.; Harding, David J.
• Is Part Of: Dalton transactions. Volume 47:Issue 35(2018)
• Page Start: 12449
• Page End: 12458
• Publication Date: 2018-08-22
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt02016g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The magnetic properties of a series of iron(iii ) complexes [Fe(naphEen)2 ]halide·sol are reported. Abstract : A series of iron(iii ) complexes [Fe(naphEen)2 ]X·sol (naphEen = 1-{[2-(ethylamino)-ethylimino]methyl}-2-naphtholate; X = F, sol = 0.5CH2 Cl2 ·H2 O1 ; sol = H2 O, X = Cl, 2 and X = Br3 ) and [Fe(naphEen)2 ]I4 has been prepared. The UV-Vis spectra reveal clear differences for1 which DFT/TDDFT calculations suggest are due to an equilibrium between [Fe(naphEen)2 ]F and [Fe(naphEen)2 F], the latter having a coordinated F ligand. The X-ray crystal structures of2–4 show LS Fe(iii ) centres in all cases and extensive aryl interactions that link the Fe centres into supramolecular squares. In3 at room temperature the compound loses half an equivalent of water resulting in a change in space group from Monoclinic P 21 / n to C 2/ c . Magnetic studies indicate that1 is trapped in a mixed spin state being ca . 40% HS while2–4 are effectively low spin up to 350 K. In contrast, Mössbauer spectroscopic studies of1 indicate a gradual but incomplete spin crossover. The magnetic properties of2–4 contrast with the related [Fe(salEen-X)2 ]anion derivatives which are often spin crossover active.