There are several substituted azupyrenes where the gap between S 1 and the triplet of the same configuration is negative -thus constituting a Hund's rule violation -but where another triplet state is lower in energy (Table ). This includes the abovementioned azupyrene-3,5,8,10-tetraol, which has an inverted gap of -3 meV, but the Hund's rule violation exists be-tween S 1 and T 2 and is at a notable E(S 1 -T 2 )=-120 meV; similar values are obtained for the analogous amine-and methoxysubstituted molecules. The tetrakis(trifluoromethyl)-substituted azupyrene has a more negative gap than azupyrene-1,2,6,7tetracarbonitrile at the CC2/cc-pVDZ level, but we were not able to obtain a result with the EOM-CCSD method due to the size of the molecule. There is potentially a huge chemical space to explore with larger substituents that may enable inverted singlettriplet gaps in azupyrenes.