Switching the Macrocycle Conformation from Nonplanar to Planar in Cobalt(II) and Copper(II) β-Tetra-2′-thienyl-meso-tetraphenylporphyrin Cocrystallates with C60

Crystal structures of cobalt(II) and copper(II) complexes of 2,3,12,13-tetra-2'-thienyl-5,10,15,20-tetraphenylporphyrin/C-60 cocrystallates were determined by single-crystal XRD analysis. The crystal structures of the two cocrystallates, MTPP(2'-thienyl) 4 center dot C-60 center dot(toluene) 2 (M = Co-II and Cu-II; TPP = tetraphenylporphyrin), compounds 1 and 2, respectively, are isomorphous and reveal a one-dimensional (1D) supramolecular structure. In these cocrystallates, the macrocycle is almost planar within +/- 0.08 angstrom, as evidenced by comparing the value of Delta C-b (the average deviation of the beta-pyrrole carbon from the porphyrin ring mean plane) with those for the nonplanar parent structures, CoTPP(2'-thienyl) 4 [+/- 0.710(5) angstrom] and CuTPP(2'-thienyl) 4 [+/- 0.546(2) angstrom]. This difference has been ascribed to intermolecular interactions and/or crystal packing forces.