Triplet fluoranthenes: Aromaticity versus unpaired electrons.

Three fluoranthenes and one substituted fluoranthene, 2,2-dimethyl-2 H-dibenzo[ cd,k]fluoranthene, were investigated using the unrestricted symmetry-broken and complete active space methods. It was shown that four Kekuléan hydrocarbons are diradicals, implying that their ground state is a triplet. In the energetically less favorable singlet state these hydrocarbons exhibit pronounced diradical character. This occurance is explained with the tendency of the investigated molecules to delocalize their π-electrons. This leads to aromatic stabilization which is stronger than destabilization due to unpaired electrons. Our results for 2,2-dimethyl-2 H-dibenzo[ cd,k]fluoranthene are in excellent accord with experimental findings of McMaster et al. concerning this compound. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]