CONSEQUENCES OF OXIDATION IN NONPLANAR PORPHYRINS - MOLECULAR-STRUCTURE AND DIAMAGNETISM OF THE PI-CATION-RADICAL OF COPPER(II) OCTAETHYLTETRAPHENYLPORPHYRIN

Crystal structures are reported for the sterically crowded porphyrin C opper(II) 2,3,7,8,12,13, 17,18-octaethyl-5,10,15,20-tetraphenylporphyr in (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 shoul d also prevent the dimerizations in the solid that have complicated se veral previous crystallographic studies of porphyrin pi cation radical s. Interest in the consequences of oxidation arises from the presence of nonplanar bacteriochlorophylls in photosynthetic reaction centers i n which the chromophores lie van der Waals contact so that even small structural changes induced by electron transfer would alter the electr onic coupling between the pi cation and anion radicals generated by th e 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 ring s twist, the meso carbons move alternately up and down out of the porp hyrin plane by similar to 0.2 Angstrom, and the phenyl groups rotate f urther into that plane by more than 10 degrees. The additional distort ions 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 s olution 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 p orphyrin pi cation radicals comprised of paramagnetic metals control m agnetic coupling with the metals and that nonplanar macrocycles exhibi t antiferromagnetic coupling. 2 displays optical and FT-IR spectral si gnatures diagnostic of a pi cation radical in solution, but it is EPR- silent, and its NMR spectrum clearly indicates a diamagnetic species. The Cu(II) and the nonplanar pi radical spins in 2 are thus indeed ant iferromagnetically coupled, in accord with the above proposal. The sad dle conformation of 1 destabilizes the pi system of the macrocycle and causes the molecule to be readily oxidized with molecular iodine, a m ild oxidizing agent. Unexpectedly, the radical crystallized in the pre sence of excess I-2 carries a discrete I-7(-) counterion. We report he re the first example and structure of such a large polyiodide union to be stabilized by a porphyrin cation: Cu(OETPP)I-.+(7-) (3). Crystallo graphic data. CuN4C60H60 (1): triclinic space group <P(1)over bar>, a = 13.888(4) Angstrom, b = 16.820(3) Angstrom, c = 13.222(3) Angstrom, alpha = 97.33(2)degrees, beta = 107.97(2)degrees, gamma = 103.52(2)deg rees, V = 2843.3 Angstrom(3), Z = 2, R(F) = 0.057 and R(wF) = 0.086 ba sed on 7391 reflections with F-o > 3 sigma F-o, T = 298 K. (CuN4C60H60 ClO)-Cl-.+(-)(4).CH2Cl2 (2): monoclinic space group P2(1)/n, a = 11.89 6(1) Angstrom, b = 24.242(5) Angstrom, c = 19.090(3) Angstrom, beta = 100.73(1)degrees, V = 5408.8 Angstrom(3), Z = 4, R(F) = 0.048 and R(wF ) = 0.049 based on 4570 reflections with F-o > 3 sigma F-o, T = 298 K. (BBCuN4C60H60I7-)-I-.+ (3): monoclinic space group P2(1), a = 13.108( 17) Angstrom, b = 18.332(14) Angstrom, c = 13.683(10) Angstrom, beta = 107.88(8)degrees, V = 3129.2 Angstrom(3), Z = 2, R(F) = 0.101 and R(w F) = 0.117 based on 2269 reflections with F-o > 4 sigma F-o, T = 200 K .