Supramolecular fullerene-porphyrin chemistry. Fullerene complexation by metalated jaws porphyrin hosts

Porphyrins and fullerenes are spontaneously attracted to each other. This new supramolecular recognition element is explored in discrete, soluble, coordinatively linked porphyrin and metalloporphyrin climers, Jawlike clefts in these bis-porphyrins are effective hosts for fullerene guests. X-ray structures of the Cu complex with C-60 and free-base complexes with C-70 and a pyrrolidine-derivatized C-60 have been obtained. The electron-rich 6:6 ring-juncture bonds of C-60Z show unusually close approach to the porphyrin or metalloporphyrin plane. Binding constants in toluene solution increase in the order Fe(II) < Pd(II) < Zn(II) < Mn(II) < Co(II) < Cu(II) < 2H and span the range 490-5200 M-1. Unexpectedly, the free-base porphyrin binds C-60 more strongly than the metalated porphyrins. This is ascribed to electrostatic forces, enhancing the largely van der Waals forces of the pi-pi interaction. The ordering with metals is ascribed to a subtle interplay of solvation and weak interaction forces. Conflicting opinions on the relaflve importance of van der Waals forces, charge transfer, electrostatic attraction, and coordinate bonding are addressed. The supramolecular design principles arising from these studies have potential applications in the preparation of photophysical devices, molecular magnets, molecular conductors, and porous metal-organic frameworks.