From overcrowded polycyclic aromatic enes to semifullerenes

Overcrowded polycyclic aromatic enes (1), e.g., bi-9H-fluoren-9-ylidene (2) and bi-4H-cyclopenta[def]-phenanthren-4-ylidene (3) are potential starting materials for the preparation of bowl-shaped fragments of fullerenes. Semiempirical MNDO-PM3 calculations of C₂₆H_n and C₃₀H_n (n = 12, 14, 16) species 2-14 are used to analyze energetic and steric effects on the dehydrocyclization and isomerization reactions of these molecules. The out-of-plane bending and pyramidalization in these species are ascribed to intramolecular overcrowding in the fjord and cove regions and to strain introduced by C5 rings in the PAH skeleton. Oxidative photocyclization reactions on Z-2,2′-bridged derivatives of 2 and 3 are briefly outlined.