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Inhibition of intermolecular interactions by steric substituents allows detailed investigation of the electronic structure arising from the planar geometry of the d<jats:sup>6<\/jats:sup> electron configuration. Complementary magnetometry, M\u00f6ssbauer, FD\u2010FT THz\u2010EPR (frequency\u2010domain Fourier\u2010transform terahertz electron paramagnetic resonance) and pNMR (nuclear magnetic resonance of paramagnetic molecules) spectroscopies show that FePc<jats:sup>OAr<\/jats:sup> has an <jats:italic>S\u00a0<\/jats:italic>=\u00a01 ground state with large positive axial zero\u2010field splitting (ZFS) and a strongly anisotropic <jats:italic>g<\/jats:italic>\u2010tensor, with two <jats:italic>g<\/jats:italic>\u2010values much larger than the free electron <jats:italic>g<\/jats:italic>\u2010value and one smaller. Correlation between the magnetic properties and the electronic structure is provided by high\u2010level quantum chemical calculations. The calculations indicate a nearly triply degenerate ground level, in which spin\u2010orbit coupling mixes the isolated <jats:sup>3<\/jats:sup>A<jats:sub>2g<\/jats:sub> ground state with two excited <jats:sup>3<\/jats:sup>E<jats:sub>g<\/jats:sub> states, whose energy gaps to the ground state are almost identical. These findings provide valuable insights in the electronic structure of iron phthalocyanines and the long\u2010standing discussion on their true electronic ground level, which has important implications for the application of this important class of complexes in catalysis and magnetic materials.<\/jats:p>","DOI":"10.1002\/chem.202501474","type":"journal-article","created":{"date-parts":[[2025,5,28]],"date-time":"2025-05-28T05:42:35Z","timestamp":1748410955000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Electronic and Magnetic Properties of Ferrous Iron in a True Square\u2010Planar Molecular Environment"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-3658-031X","authenticated-orcid":false,"given":"Tim Marcel","family":"Diederich","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry Heidelberg University  Im Neuenheimer Feld 270 69120 Heidelberg 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