Based on the chemist's interpretation of Kasha's rule that prohibits photochemistry from higher order excited states, we therefore irradiated the reactions forming 3aa and 3gb with commercially-available LEDs at 740 nm and 850 nm and were mystified to observe no reaction in either case (Figure ). That successful reaction was only observed at 400 nm implicated anti-Kasha behavior; a higher-order excited state participated in SET photooxidation. Greatly aiding our mechanistic study of this phenomenon was the fact that TPA .+ s can be preparatively isolated as their bench stable PF6 salts. (65) Their XRD crystal structures revealed a common propeller-type structure, also observed for parent TPAs (Figure ). However, attempts to investigate quenching of photoexcited TPA .+ s were thwarted by the fact that they do not exhibit steady-state fluorescence (see Supplementary Information). Consistent with this observation, the reported lifetimes of related excited N radical cation species (74-76) lie within the femto-to picosecond timeframe. As a result, transient absorption spectroscopy (TAS) was employed to determine the lifetimes of excited TpBPA .+ and TCBPA .+ . Pumping with a broadband visible light source (490-900 nm) revealed a ground state bleach in the 600-850 nm bands (Figure ) and an excited state absorption between 490-570 nm, indicative of absorption by the D1 (or D2) excited states. The lifetimes of the D1 excited states of TpBPA .+ and TCBPA .+ were 4.6 ps and 8.6 ps, respectively, clearly ruling out photochemistry by diffusion-control and bimolecular quenching. It is reasonable to assume that higher order excited states possess even shorter lifetimes, and that precomplexation can therefore be the only rationalization for productive, unimolecular SET and the aforementioned anti-Kasha behaviour. Presuming that precomplexes may possess different UV-vis absorption than their parent TPA .+ s, we investigated quenching of the absorption of TPA .+ s in the presence of representative concentrations of arenes (Figure ). In the presence of mesitylene, the spectrum of TpBPA .+ was unchanged.