Doubly Fused Unsymmetrical Calixdicarbahexaphyrins.

Three novel doubly fused unsymmetrical calixdicarbahexaphyrins were synthesized by mild acid-catalyzed (4+2) condensation of dicarbatetrapyrrane with dipyrroethene diol followed by oxidation. The condensation formed doubly fused calixdicarbahexaphyrins instead of π-conjugated dicarbahexaphyrins, due to the unusual fusion of the pyrrole N with the α-carbon of the adjacent pyrrole ring to form a tripentacyclic ring and one usual fusion of the pyrrole N with the adjacent phenylene C to form a fused moiety containing two pentacycles and one hexacycle ring. Both fusions occurred on one side of the macrocycle, making the macrocycles unsymmetric. The crystal structure obtained for one of the macrocycles exhibited a saddle-shaped structure with two benzene rings and four pyrrole rings connected via two ethylene and four methene