Similar to bicalicene (Figure ) and the constrained D 2h sindacene and C 2v indeno[1,2,3-e f ]heptalene, our approach reveals several molecules with Hund's rule violations between the lowest excited singlet state and a higher-lying excited triplet state of the same electron configuration. The triplet state with the same electron configuration as the S 1 state is often not the T 1 , as there can be intruding states with a different electron configuration that has lower energy, making those the first excited triplet state. While ideally we search for molecules with inverted singlettriplet gaps, a Hund's rule violation is by definition one which occurs between electronic states with identical electron configuration. Given the fundamental interest in such molecules, we highlight more examples of higher-lying Hund's rule violations that are achieved by stabilizing the double-bond delocalized structures through substitution, as shown in Figure . The heptalenic analog of s-indacene, benzo[1,2:4,5]di [7]annulene, is stabilized in a high-symmetry structure by both electron-donating (amine) and electronaccepting (borane) groups at the LUMO and HOMO positions, respectively. This leads to large Hund's rule violations of -305 and -165 meV, respectively. While it is planar in the unsubstituted (C 2h ) and amine-substituted (quasi-D 2h ) forms, borane functionalization at the central 6-membered ring induces out-of-plane distortion to the ring system into C 2 symmetry. To our knowledge, benzo [1,2:4,5]di [7]annulenes have not been synthesized.