Monophotonically UV excited delayed luminescence in rigid solutions of aromatic amines

During a study of neutralization luminescence following photoionization of aromatic solutes in rigid organic glasses, a new type of long-lived luminescence has been observed simultaneously with the well-known neutralization luminescence following biphotonic ionization. It has been extensively studied for tetramethyl-p-phenylenediamine in methylcyclohexane or ethanol: it is one-photon excited but differs from the ordinary luminescence by the emission spectrum (λ_max 430 nm compared to λ_{max f.} 395 nm and λ_{max ph.} 490 nm in ethanol) and by the excitation spectrum, the present luminescence being observed only for short wavelength excitation. Finally the lifetime (of the order of seconds) depends on experimental conditions. Other solid and liquid phase studies suggest that the precursor of this new luminescence is a solute-solvent charge transfer state.