Excited-state singlet-triplet inversion in hexagonal aromatic and heteroaromatic compounds

The inversion of the energies of the lowest singlet (S 1 ) and lowest triplet (T 1 ) excited states in violation of Hund's multiplicity rule is a rare phenomenon in stable organic molecules. S 1 -T 1 inversion has significant consequences for the photophysics and photochemistry of organic chromophores. In this work, wave-function based ab initio computational methods were employed to explore the possibility of S 1 -T 1 inversion in hexagonal polycyclic aromatic and heteroaromatic compounds. In these molecules, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are two-fold degenerate. The HOMO-LUMO transition gives rise to three singlet and three triplet excited states. While the singlet-triplet energy gap Δ ST , defined as the energy difference between the S 1 state and the T 1 state, is clearly positive for benzene, it is predicted to be close to zero for borazine, the boron nitride analogue of benzene. Although Δ ST decreases with increasing size of hexagonal polycyclic aromatics, it remains positive up to circumcoronene (19 rings). However, symmetry-preserving substitution of C-C pairs by B-N groups in the interior, keeping the conjugation of the outer rim intact, results in compounds with robustly negative Δ ST . These findings establish the existence of a new family of boron carbon nitrides with inverted singlet-triplet gaps. The inversion of the energies of the lowest singlet (S 1 ) and lowest triplet (T 1 ) excited states in violation of Hund's multiplicity rule is a rare phenomenon in stable organic molecules.