The relative energies of selected states for one-electron oxidized difluoro(porphinato)iron(III) and fluoro(porphinato)iron(III) have been studied using approximate density functional methods. For the difluoro derivative an iron(IV) (S=1) state is stabilized relative to an iron(III) A2u p-cation radical (S=3) state. For the monofluoro species this ordering of states is reversed. The molecular structures of difluoro(porphinato)iron(III) and the corresponding iron(IV) and iron(III) A2u p-cation radical species have been investigated using a full geometry optimization. The A2u p-cation radical species has a geometry very similar to the parent compound. In contrast, the iron(IV) derivative displays significantly shortened Fe-N and Fe-F bond distances. A possible relationship between iron(III) spin-state and the site of one-electron oxidation in iron(III) porphyrins is rationalized in terms of exchange energy stabilization and the s- and p-donor properties of the axial ligand(s). The pÆp* singlet transition energies of chloro(porphinato)iron(III) have been calculated. Good agreement with experimental values is found and an assignment of the Q-band region as arising from 14a1Æ18e (a2uÆeg* ) and 5a2Æ18e (a1uÆeg*) transitions is proposed. The B-band (Soret) region is suggested to arise from 8b1Æ18e (b2uÆeg*) and 13a1Æ18e (a2u'Æeg*) transitions.