Gary J. Long

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O ₂ to form high-spin iron(IV)=O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O ₂ at low temperatures to form high-spin iron(IV)=O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O ₂ , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.

The Mössbauer spectra of trigonal α-FePO₄, measured between 4.2 and 300 K, exhibit hyperfine parameters characteristic of high-spin iron(III) in a pseudotetrahedral oxygen environment. Between 24.5 and 300 K, the spectra show a paramagnetic quadrupole doublet and at 24.0 K the spectrum reveals the onset of antiferromagnetic exchange. At 4.2 and 16 K, a single magnetic sextet is observed with hyperfine fields of 51.36(1) and 42.74(1) T, respectively, with an angle, θ, of 90° between the principal axis of the electric field gradient tensor in the basal plane of the trigonal unit cell and the hyperfine field along the c axis. The spectra obtained between 21 and 18 K have been fitted with two equal-area magnetic sextets with θ angles of 25 and 85°, angles which indicate that the iron(III) magnetic moments are canted away from the c axis. The reduced hyperfine field versus reduced temperature plot indicates a departure from a Brillouin S = 5/2 behavior, as a result of some magnetostriction at the Néel temperature. The Mössbauer spectra of class 1 mixed-valence SrFe₃(PO₄)₃, measured between 4.2 and 300 K, exhibit hyperfine parameters characteristic of two high-spin iron(II) ions and one high-spin iron(III) ion in a pseudooctahedral oxygen environment. At and above 40 K, the spectra show two paramagnetic quadrupole doublets, whereas at 39.0 K the spectrum reveals the onset of ferrimagnetic exchange. Between 4.2 and 30 K, the spectra have been fitted with two magnetic sextets with θ angles of 85 and 10° for the iron(II) and iron(III) sites, respectively. The reduced hyperfine field versus reduced temperature plots for the iron(II) and iron(III) sites show a distinct departure from Brillouin S = 2 and S = 5/2 behavior, respectively, a departure that suggests a first-order magnetic transition at 39.5(5) K with differing magnetostrictions at the iron(II) and iron(III) sites.