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 S₁ and triplet T₁ 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 S₁ and T₁. 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 S₁–T₁ gap. We also determined the 0–0 energies to evaluate the significance of the vertical approximation. In addition, we compute reference S₁–T₁ 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.