Formation and isomerization of dicyclopenta[de,mn]anthracene. Electronic structure study.

The formation of dicyclopenta[de,mn]anthracene (P1) and its isomerization into dicyclopenta[jk,mn]phenanthrene (P3) was investigated using density functional theory. It was shown that P1 is formed from 1,4-diethynilanthracene, but due to its instability, it undergoes further transformation. This transformation involves rearrangements of some hydrogen atoms and ring contraction/ring expansion process, yielding as a final product the isomer P3. The energies of activation for the P1-->P3 intraconversion show that this reaction is competitive to the other, previously investigated isomerization of P1 into dicyclopenta[de,kl]anthracene (P2). In addition, our investigation shows that the formation of P3 from P1 is energetically more favorable than the formation of P3 from P2. Thus, the presence of the isomer P3 in the reaction mixtures could also be caused by the isomerization of the very unstable isomer P1.