Crystal structures are reported for the sterically crowded porphyrin Copper(II) 2,3,7,8,12,13, 17,18-octaethyl-5,10,15,20-tetraphenylporphyrin (Cu(OETPP), 1) and its pi cation radical Cu(OETPP)(ClO4-)-Cl-.+ (2). 1 was chosen to assess the consequences of oxidation in a nonplanar porphyrin on the expectation that its multiple peripheral substituents not only induce an S4 saddle conformation on the macrocycle but should also prevent the dimerizations in the solid that have complicated several previous crystallographic studies of porphyrin pi cation radicals. Interest in the consequences of oxidation arises from the presence of nonplanar bacteriochlorophylls in photosynthetic reaction centers in which the chromophores lie van der Waals contact so that even small structural changes induced by electron transfer would alter the electronic coupling between the pi cation and anion radicals generated by the primary photochemical charge separation. Oxidation of 1 does indeed result in further conformational changes in 2 : an additional ruffling is imposed on the original saddle shape of 1 in which the pyrrole rings twist, the meso carbons move alternately up and down out of the porphyrin plane by similar to 0.2 Angstrom, and the phenyl groups rotate further into that plane by more than 10 degrees. The additional distortions are attributed to changes in electronic configuration due to the oxidation and to the low-energy barriers between nonplanar conformers with different degrees of nonplanarity predicted by previous molecular mechanics calculations. OETPPs retain their saddle conformations in solution because of the steric crowding of the multiple substituents. 2 thus provides a test of the proposal by Reed, Scheidt, and co-workers (e.g., J. Am. Chem. Soc. 1987, 109, 2644) that the conformations of porphyrin pi cation radicals comprised of paramagnetic metals control magnetic coupling with the metals and that nonplanar macrocycles exhibit antiferromagnetic coupling. 2 displays optical and FT-IR spectral signatures diagnostic of a pi cation radical in solution, but it is EPR-silent, and its NMR spectrum clearly indicates a diamagnetic species.