Electronic structure of a series of five-coordinate Fe ( OArTAzP ) X ( OAr = octaaryltetraazaporphyrin , X = Cl-, Br-, I-; Ar = 4-tert-butylphenyl) have been examined on the basis of1H NMR,13C NMR, and EPR spectroscopy as well as SQUID magnetometry. These complexes adopt the intermediate-spin state as in the case of analogous complexes reported by Fitzgerald et al. (Inorg. Chem. 1992; 31: 2006-2013) and Stuzhin et al. (Inorg. Chim. Acta 1995; 236: 131-139). The13C NMR studies using13C -enriched complexes at the pyrrole α positions have revealed that the pyrrole- Cαsignals appear at extraordinary upfield positions, i.e. -130 to -250 ppm at 273 K, due to the dz2-a2 uand dπ-3 eginteractions. The Curie plots of the pyrrole- Cαsignals have further revealed that the iodide complex adopts a much purer intermediate-spin state than the bromide and chloride complexes. In contrast to the case of Fe ( OArTAzP ) X , six-coordinate [ Fe ( OArTAzP )( CN )2]-showed the pyrrole- Cαsignal at 47 ppm at 273 K, which indicates that the complex adopts the low-spin state with the ( dxy)2( dxz, dyz)3electron configuration. Thus, the13C NMR chemical shift of the pyrrole- Cαsignal turns out to be quite a good probe to elucidate the spin state and electron configuration of iron(III) tetraazaporphyrins, where the1H NMR spectroscopy is less useful because of the absence of the hydrogen atoms as well as the alkyl or aryl groups directly attached to the meso positions.
Excitonic dispersion of the intermediate spin state in
LaCoO3
revealed by resonant inelastic x-ray scattering