Accessibility and Selective Stabilization of the Principal Spin States of Iron by Pyridyl versus Phenolic Ketimines: Modulation of the ⁶A₁ ↔ ²T₂ Ground-state Transformation of the [FeN₄O₂]⁺ Chromophore


Several potentially tridentate pyridyl and phenolic Schiff bases (apRen and HhapRen, respectively) were derived from the condensation reactions of 2-acetylpyridine (ap) and 2′-hydroxyacetophenone (Hhap), respectively, with N-R-ethylenediamine (RNHCH2CH2NH2, Ren; R = H, Me or Et) and complexed in situ with iron(II) or iron(III), as dictated by the nature of the ligand donor set, to generate the six-coordinate iron compounds [FeII(apRen)2]X (R = H, Me; X- = ClO4-, BPh4-, PF6-) and [FeIII(hapRen)2]X (R = Me, Et; X- = ClO4-, BPh4-). Single-crystal X-ray analyses of [FeII(apRen)2](ClO4)2 (R = H, Me) revealed a pseudo-octahedral geometry about the ferrous ion with the FeII-N bond distances (1.896-2.041 Å) pointing to the 1A1 (dπ6) ground state; the existence of this spin state was corroborated by magnetic susceptibility measurements and Mössbauer spectroscopy. In contrast, the X-ray structure of the phenolate complex [FeIII(hapMen)2]ClO4, determined at 100 K, demonstrated stabilization of the ferric state; the compression of the coordinate bonds at the metal center is in accord with the 2T2 (dπ5) ground state. Magnetic susceptibility measurements along with EPR and Mössbauer spectroscopic techniques have shown that the iron(III) complexes are spin-crossover (SCO) materials. The spin transition within the [FeIIIN4O2]+ chromophore was modulated with alkyl substituents to afford two-step and one-step 6A12T2 transformations in [FeIII(hapMen) 2]ClO4 and [FeIII(hapEen)2]ClO4, respectively. Previously, none of the X-salRen- and X-sal2trien-based ferric spin-crossover compounds exhibited a stepwise transition. The optical spectra of the LS iron(II) and SCO iron(III) complexes display intense dπ → pπ* and pπ → dπ CT visible absorptions, respectively, which account for the spectacular color differences. All the complexes are redox-active; as expected, the one-electron oxidative process in the divalent compounds occurs at higher redox potentials than does the reverse process in the trivalent compounds. The cyclic voltammograms of the latter compounds reveal irreversible electrochemical generation of the phenoxyl radical. Finally, the H2salen-type quadridentate ketimine H2hapen complexed with an equivalent amount of iron(III) to afford the μ-oxo-monobridged dinuclear complex [{FeIII(hapen)}2 (μ-O)] exhibiting a distorted square-pyramidal geometry at the metal centers and considerable antiferromagnetic coupling of spins (J ≈ -99 cm-1).



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© 2012 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jul 2012