Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Baird‐Aromatic Triplet Ground State Compounds

Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed‐shell singlet state (normally ground state, S₀) and lowest ππ* triplet state (T₁ or T₀), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T₁ and S₀ states. This effect is caused by a reversal in the dipole moment when going from S₀ to T₁ as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S₀ reduces (enhances) aromaticity in T₁, allowing for rationalizations of the triplet state energies (E_T) of substituted fulvenes. Through quantum chemical calculations, we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted E_T. As a means to increase the π‐electron withdrawing capacity of cyano groups, we found that protonation at the cyano N atoms of 6,6‐dicyanopentafulvenes can be a route to on‐demand formation of a fulvenium dication with a triplet ground state (T₀). The five‐membered ring of this species is markedly Baird‐aromatic, although less than the cyclopentadienyl cation known to have a Baird‐aromatic T₀ state.