The S3-T4 state pair exhibiting the Hund´s rule violation involve a non-overlapping HOMO and LUMO of a2 symmetry localized on the cyclopentadiene and cyclopropylene fragments, respectively (blue in Figure ). These states thus constitute a charge-transfer (CT) state with 95% CT character from the 5-membered to the 3-membered ring in S3 (see Supporting Information). This differs qualitatively from the Hund´s rule violation in trans-bicalicene, in which the contributing orbitals are both located on both the 3-and 5-membered rings in an alternating fashion (Figure ), leading to only 37% inter-ring CT character in S1. The other three excited state pairs in calicene, which adhere to Hund's rule, involve two other π-type orbitals of b2 symmetry (black in Figure ). These orbitals are delocalized over the entire molecule, and therefore exhibit significant overlap with each other and with the a2 orbitals, leading to preservation of Hund´s rule in these three singlet-triplet state pairs. While a violation of Hund's rule in the excited states is of theoretical interest, it is not optically relevant for the design of optoelectronic materials. Therefore, by stabilizing the LUMO localized on the cyclopropylene fragment and destabilizing the HOMO on the cyclopentadiene relative to the delocalized b2 orbitals, we show that the energies of the singlet and triplet states violating Hund's rule can be lowered relative to the three other excited states.