The NMR and EPR spectra of a series of pyridine complexes [(OEC)Fe(L)(2)](+) (L = 4-Me2NPy, Py, and 4-CNPy) have been investigated. The EPR spectra at 4.2 K suggest that, with a decrease of the donor strength of the axial ligands, the complexes change their ground state from (d(xy))(2)(d(xz)d(yz))(3) to (d(xz)d(yz))(4)(d(xy))(1). The NMR data from 303 to 183 K show. that at any temperature within this range the chemical shifts of pyrrole-8,17-CH2 protons increase with a decrease in the donor strength of the axial ligands. The full peak assignments of the [(OEC)Fe(L)(2)](+) complexes of this study have been made from COSY and NOE difference experiments. The pyrrole-8,17-CH2 and pyrroline protons show large chemical shifts (hence indicating large 7 spin density on the adjacent carbons which are pan of the pi system), while pyrrole-12,13-CH2 and -7,18-CH2 protons show much smaller chemical shifts, as predicted by the spin densities obtained from molecular orbital calculations, both Huckel and DFT; the DFT calculations additionally show close energy spacing of the highest five filled orbitals (of the Fe(H) complex) and strong mixing of metal and chlorin character in these orbitals that is sensitive to the donor strength of the axial substituents. The pattern of chemical shifts of the pyrrole-CH2 protons of [(OEC)Fe(t-BuNC)(2)](+) looks somewhat like that of [(OEC)Fe(4-Me2NPY)(2)](+), while the chemical shifts of the meso-protons are qualitatively similar to those of [(OEP)Fe(t-BuNC)(2)](+). The temperature dependence of the chemical shifts of [(OEC)Fe(t-BuNC)(2)](+) shows that it has a mixed (d(xz)d(yz))(4)(d(xy))(1) and (d(xy))(2)(d(xz),d(yz))(3) electron configuration that cannot be resolved by temperature-dependent fitting of the proton chemical shifts, with a S = 5/2 excited state that lies somewhat more than 2kT at room temperature above the ground state; the observed pattern of chemical shifts is the approximate average of those expected for the two S = 1/2 electronic configurations, which involve the a-symmetry SOMO of a planar chlorin ring with the unpaired electron predominantly in the d(yz) orbital and the b-symmetry SOMO of a ruffled chlorin ring with the unpaired electron predominantly in the d(xy) orbital. A rapid interconversion between the two, with calculated vibrational frequency of 22 cm(-1), explains the observed pattern of chemical shifts, while a favoring of the ruffled conformation explains the negative chemical shift (and thus the negative spin density at the cc-pyrroline ring carbons), of the pyrroline-H of [TPCFe(t-BuNC)(2)]CF3SO3 (Simonneaux, G.; Kobeissi, M. J. Chem. Soc., Dalton Trans. 2001, 1587-1592). Peak assignments for high-spin (OEC)FeCl have been made by saturation transfer techniques that depend on chemical exchange between this complex and its bis-4-Me2NPy adduct. The contact shifts of the pyrrole-CH2 and meso protons of the high-spin complex depend on both sigma and pi spin delocalization due to contributions from three of the occupied frontier orbitals of the chlorin ring.