Prediction of Spin Density, Baird‐Antiaromaticity, and Singlet–Triplet Energy Gap in Triplet‐State Polybenzenoid Systems from Simple Structural Motifs

Abstract

Triplet‐state aromaticity has been recently proposed as a strategy for designing functional organic electronic compounds, many of which are polycyclic aromatic systems. However, in many cases, the aromatic nature of the triplet state cannot be easily predicted. Moreover, it is often unclear how specific structural manipulations affect the electronic properties of the excited‐state compounds. Herein, the relationship between the structure of polybenzenoid hydrocarbons (PBHs) and their spin‐density distribution and aromatic character in the first triplet excited state is studied. Although a direct link is not immediately visible, classifying the PBHs according to their annulation sequence reveals regularities. Based on these, a set of guidelines is defined to qualitatively predict the location of spin and paratropicity and the singlet–triplet energy gap in larger PBHs, using only their smaller tri‐ and tetracyclic components, and subsequently tested on larger systems.