Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet-Triplet Gap.

Molecules that violate Hund's rule and exhibit an inverted gap between the lowest singlet S and triplet T excited states have attracted considerable attention due to their potential applications in optoelectronics. Among these molecules, the triangular-shaped heptazine, and its derivatives, have been in the limelight. However, conflicting reports have arisen regarding the relative energies of S and T. Here, we employ highly accurate levels of theory, such as CC3, to not only resolve the debate concerning the sign but also quantify the magnitude of the S-T gap. We also determined the 0-0 energies to evaluate the significance of the vertical approximation. In addition, we compute reference S-T gaps for a series of 10 related molecules. This enables us to benchmark lower-order methods for future applications in larger systems within the same family of compounds. This contribution can serve as a foundation for the design of triangular-shaped molecules with enhanced photophysical properties.