Abstract
The electronic structures, and, particularly, the nature of the HOMO in a series of the low-spin PcFeL2, PcFeL′L″, and [PcFeX2]2- iron(II) phthalocyanine complexes were probed by electrochemical, spectroelectrochemical and chemical oxidation approaches and complimented by MCD spectroscopy as well as theoretical (DFT and TDDFT) studies. In general, energies of the metal-centered occupied orbitals in the various six-coordinate iron phthalocyanine complexes correlate well with Lever’s electrochemical parameter, EL, and intercross the phthalocyanine-centered a1u orbital in several compounds with moderate-to-strong p-accepting axial ligands. In these cases, an oxidation of the phthalocyanine macrocycle (Pc(2-)/Pc(1-)) rather than the central metal ion (Fe(II)/Fe(III)) was theoretically predicted and experimentally confirmed. The experimentally derived using MCD spectroscopy or theoretically predicted using TDDFT calculations energy of the MLCT1 transition (dπ→Pc(π*)) on iron(II) phthalocyanines also follows the trend expected for the EL properties of the axial ligands.
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