Interaction of Curved and Flat Molecular Surfaces. The Structures of Crystalline Compounds Composed of Fullerene (C60, C60O, C70, and C120O) and Metal Octaethylporphyrin Units

Solutions of C 60, C 60 O, or C 70 and metal complexes of octaethylporphyrin (OEPH 2 ) yield crystals that contain both the fullerene and the porphyrin. The structures of C 60 ·2Co II (OEP)·CHCl 3, C 60 ·2Zn II (OEP)·CHCl 3, and C 60 O·2Co II (OEP)·CHCl 3 are isomorphous and contain an ordered C 60 cage surrounded by two M II (OEP) units. Although there is no covalent bond between the fullerene and porphyrin components, the separation between these units is shorter than normal van der Waals contact. Crystals of C 70 ·Co II (OEP)·C 6 H 6 ·CHCl 3, C 70 ·Ni II (OEP)·C 6 H 6 ·CHCl 3, and C 70 ·Cu II (OEP)·C 6 H 6 ·CHCl 3 are also isomorphous with an ordered fullerene, but have only one porphyrin/fullerene contact. Crystalline C 60 ·ClFe III (OEP)·CHCl 3 lacks the close face-to-face porphyrin/porphyrin contact that is common to all of the other structures reported here but retains the intimate contact between the porphyrin and the fullerene. In (C 120 O)·Co II (OEP)·0.6C 6 H 6 ·0.4CHCl 3 the fullerene dimer is enclosed by two Co II (OEP) moieties. Unfortunately disorder in the fullerene portion obscures details of the geometry of the bridging region between the fullerenes.