Syntheses, structural studies, electrochemistry, and spectroscopy of a number of [5,10,15,20-tetrakis(heptafluoropropyl)porphinato]iron derivatives are presented. The X-ray crystal structure of 5,10,15,20-tetrakis(heptafluoropropyl)porphinato]iron(II).(pyridine)(2) exhibits a substantial Sq distortion of the porphyrin macrocycle, with the meso-carbon atoms displaced more than 0.6 Angstrom above and below the porphyrin mean plane defined by the four central nitrogen atoms; the most notable aspect of this ferrous porphyrin structure is the fact that it exhibits metrical features commonly manifested in crystallographically characterized ferric porphyrin complexes. X-ray data are as follows: P2(1)/n with a = 12.772(1) Angstrom, b = 18.895(2) Angstrom, c = 19.756(2) Angstrom, beta = 99.960(6)degrees, V = 4695.7(8) Angstrom(3), Z = 4, and d(calc) = 1.689 g/cm(3). F-19 NMR spectroscopy confirms the sensitivity of the F-19 nucleus as a probe of macrocycle aromaticity and electronic structure, while H-1 NMR spectroscopic studies show large isotropic shifts for the beta-protons of the (porphinato)iron(III) chloride derivative (delta = 101.5 and 86.4 ppm). Electrochemical data obtained from cyclic voltammetric and spectroelectrochemical experiments reveal that the E-1/2 value for the Fe-II/III redox couple for 5,10,15,20-tetrakis(heptafluoropropyl)por iron (pyridine)(2) is shifted by 550 mV relative to that observed for the corresponding (porphinato)iron(III) chloride complex. The cathodic electrochemistry of [5,10,15,20-tetrakis(heptafuoropropyl)porphinato]-iron(III).(pyridine)(2) is also unusual in that the first one-electron reduction of this complex produces a largely macrocycle-localized radical anion. EPR spectroscopic data shows that 5,10,15,20-tetrakis(heptafluoropropyl)por iron(III).(pyridine)(2) manifests a pure axial spectrum (Delta/lambda = -26.4; Sigma g(2) = 12.53) congruent with a (d(xz),d(yz))(4)(d(xy))(1) electronic ground state. The extraordinary structural, potentiometric, and spectroscopic properties of these (porphinato)iron species arise from substantially reduced metal-centered electron density effected by the macrocycle's non-pi-conjugating, sigma-electron-withdrawing meso-perfluoroalkyl substituents.