Effect of the Ruffled Porphyrin Ring on Electronic Structures: Structure and Characterization of [Fe(TalkylP)(OClO₃)] and [Fe(TPrP)(THF)₂]ClO₄ (alkyl = Ethyl, Et and n-Propyl, Pr)

We report the synthesis of Fe(TalkylP)(OClO₃)] (alkyl = ethyl and propyl) and [Fe(TPrP)(THF)₂]ClO₄, which are characterized by UV-vis, EPR, X-ray crystallography, and solid-state magnetic susceptibilities. The macrocycles of all three complexes are ruffled, all of the structural features for [Fe(TEtP(OClO₃)] and [Fe(TPrP)(OClO₃)] are characteristic of the nearly pure S = 3/2 state, while the structural parameters for [Fe(TPrP)(THF)₂]ClO₄ feature a pure intermediate-spin (S = 3/2) state, which are all consistent with EPR and magnetic data. It is clear from these studies that the ruffled conformation plays a significant role in affecting the extent of S = 3/2 character.