Research Papers in Physics and Astronomy


Date of this Version



Inorganic Chemistry 51:15 (2012)


The authors declare no competing financial interest.


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 com-plexed 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]X2 (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 dis-tances (1.896–2.041 Å) pointing to the 1A1 (dπ6) ground state; the existence of this spin state was cor-roborated 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 sta-bilization 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 Möss-bauer 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 substit-uents 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 Xsal2trien-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 com-pounds 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).