Synthesis, crystal structure, and photodynamics of π-expanded porphyrin-fullerene dyads synthesized by Diels-Alder reaction.

Free base and zinc porphyrins are linked with fullerene (C(60)) through β,β'-pyrrolic positions rather than meso-positions by Diels-Alder reaction of monoanthraporphyrins (H(2)P-mA and ZnP-mA) and C(60) to afford a π-expanded free base porphyrin-fullerene dyad (H(2)P-C(60)) and its zinc porphyrin-fullerene dyad (ZnP-C(60)) in 86 and 51% yield, respectively. The X-ray crystallographic analysis of ZnP-C(60) showed two comma-shaped swirls-like structure in a unit cell. The intramolecular center-to-center and edge-to-edge distances between the porphyrin and fullerene moieties were 11.

Synthesis and characterization of tetraanthroporphyrins.

Linearly pi-expanded novel tetraanthroporphyrins with and without aromatic rings at the meso-positions were prepared quantitatively for the first time from the corresponding precursors by a retro-Diels-Alder reaction.