Naturally assembling cocrystallates of C 60 and C 70 fullerenes with tetraphenylporphyrins (H 2 TPP‚C 60 ‚3 toluene, 1; H 2 T 3,5-dibutyl PP‚C 60 , 2; H 2 T 3,5-dimethyl PP‚1.5C 60 ‚2 toluene, 3; H 2 T piv PP‚C 60 , 4; H 2 T 3,5-dimethyl PP‚C 70 ‚4 toluene, 5; ZnTPP‚C 70 , 6; NiT 4-methyl PP‚2C 70 ‚2 toluene, 7) show unusually short porphyrin/fullerene contacts (2.7-3.0 Å) compared with typical π-π interactions (3.0-3.5 Å). In the C 60 structures, an electron-rich, 6:6 ring juncture, C-C bond lies over the center of the porphyrin ring. In the C 70 structures, the ellipsoidal fullerene makes porphyrin contact at its equator rather than its poles; a carbon atom from three fused six-membered rings lies closest to the center of the porphyrin. These structures provide an explanation for the manner in which tetraphenylporphyrin-appended silica stationary phases effect the chromatographic separation of fullerenes. The interaction of the curved π surface of a fullerene with the planar π surface of a porphyrin, without the need for matching convex with concave surfaces, represents a new recognition element in supramolecular chemistry. NMR measurements show that this interaction persists in toluene solution, suggesting a simple way to assemble van der Waals complexes of donor-acceptor chromophores.

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Germanium(III) corrole complex: reactivity and mechanistic studies of visible-light promoted N-H bond activationsFang, H.; Ling, Z.; Lang, K.; Brothers, P.J.; de Bruin, B.; Fu, X.