Persistent Room-Temperature Radicals from Anionic Naphthalimides: Spin Pairing and Supramolecular Chemistry

N-Substituted naphthalimides (NNIs) have been shown to exhibit highly efficient and persistent room-temperature phosphorescence from an NNI-localized triplet excited state, when the N-substitution is a sufficiently strong donor and mediates an intramolecular charge-transfer (ICT) state upon photo-excitation. This work shows that, when the electron-donating ability of the N-substitution is further increased in the presence of a carbanion or phenoxide, spontaneous electron transfer (ET) occurs and results in radical anions, verified with electron-paramagnetic resonance (EPR) spectroscopy. However, the EPR-active anion is surprisingly persistent and impervious to nucleophilic and radical reactions under anionic conditions. The stability is thought to originate from an intramolecular spin pairing between the N-donor and the NI acceptor post ET, which is demonstrated in supramolecular chemistry.