Effect of Exocyclic Substituents and π-System Length on the Electronic Structure of Chichibabin Diradical(oid)s

The ground state (GS) of Chichibabin's polycyclic hydrocarbons (CPHs) can be singlet [open- or closed-shell (OSS or CS)] or triplet (T), depending on the elongation of the π-system and the exocyclic substituents. CPHs with either a small singlet-triplet energy gap (ΔE _ST) or even a triplet GS have potential applications in optoelectronics. To analyze the effect of the size and exocyclic substituents on the nature of the GS of CPHs, we have selected a number of them with different substituents in the exocyclic carbon atoms and different ring chain lengths. The OPBE/cc-pVTZ level of theory was used for the optimization of the systems. The aromaticity of the resulting electronic structures was evaluated with HOMA, NICS, FLU, PDI, I_ring, and MCI aromaticity indices. Our results show that the shortest π-systems (one or two rings) have a singlet GS. However, systems with three to five rings favor OSS GSs. Electron-withdrawing groups (EWGs) and aromatic substituents in the exocyclic carbons tend to stabilize the OSS and T states, whereas electron-donating groups slightly destabilize them. For CS, OSS, and T states, aromaticity measures indicate a gain of aromaticity of the 6-membered rings of the CPHs with the increase in their size and when CPHs incorporate EWGs or aromatic substituents. In general, the CPHs analyzed present small singlet-triplet energy gaps, and in particular, the ones containing EWGs or aromatic substituents present the smallest singlet-triplet energy gaps.