CT-type inversion of the S1 and T1 state has been discussed previously different contexts. Bonačić-Koutecký and Michl have observed that a highly twisted zwitterionic aminoborane (H2B-NH2, Figure )corresponding to its relaxed S1 geometry -yields a negative gap using configuration interaction. These states are described by an electron transfer mechanism between the occupied nitrogen p-orbital lying at a 90 • dihedral angle to the unoccupied boron p-orbital. The coupled-cluster-based methods we report here predict a small positive gap (50 meV) for aminoborane in its relaxed S1 geometry (Table ). However, with a small structural perturbation (methylation at both B and N), the orthogonal geometry is preserved in the S1 state and the gap becomes negative at the EOM-CCSD/cc-pVDZ level (-9 meV, Table ). By contrast, the calicene derivatives reported here are both organic and planar. Unlike CT states formed via couplings between orthogonal donor and acceptor fragments, the states violating Hund's rule here are not true dark states, but instead exhibit some oscillator strength (Table ).