An earlier computational study (CASPT2/pVDZ) by Winter et al. predicts the 3,5-bis(dimethylamino)benzyl cation to have nearly degenerate singlet and triplet states. Through product studies it is demonstrated that photolysis of 3,5-bis(dimethylamino)benzyl alcohol and its corresponding acetate and phenylacetate esters in alcoholic solvents produces a solvent incorporated adduct, 3,5-bis(dimethylamino)benzyl ethers, and 3,5-bis(dimethylamino)toluene.

Calculations at the DFT level predict that benzyl anions with strong π-electron-withdrawing groups in the meta position(s) have low energy diradical or triplet electronic states. Specifically, the 2-(3,5-dinitrophenyl)-1,3-dithiane carbanion is predicted to have nearly degenerate singlet and triplet states at the (U)B3LYP level as a free anion. Its lithium ion pair is predicted to be a ground-state triplet with a substantial (26 kcal/mol) singlet-triplet energy gap. Experiments on this anion using chemical trapping, NMR, and the Evans method strongly suggest that this anion is either a triplet or a ground-state singlet with a very low energy triplet state.

Anilide anions derived from deprotonation of 4-nitroaniline and 3,5-dinitroaniline were examined by using DFT calculations, as well as ultraviolet and 1 H NMR experiments. The calculations indicate that the free anions are ground state singlets. However, when coordinated to a Li counterion, the 3,5-dinitroanilide anion is predicted to have a very narrow gap between the singlet and the triplet state. Spectroscopic data is consistent with this prediction. The UV-Vis spectrum of this anion shows a maximum absorbance at approximately 310 nm, which is in reasonable agreement with the spectrum for the singlet anion calculated by time-dependent density functional theory. On the other hand, NMR peak broadening and a modest Evans shift are consistent with the thermal population of a small amount of triplet anion.