Figure shows the steady-state emission spectra in toluene glass at 77 K. The prompt fluorescence spectra in Figure were extracted from the difference between the steady-state emission and phosphorescence spectra at 77 K. The prompt fluorescence is observed as a weak high-energy shoulder of the steady-state emission. Such behaviour implies that at low temperature the main channel of deactivation of the singlet excited state is intersystem crossing (ISC) that leads to the population of the triplet state. When compared with the 300 K steady-state PL spectra, we note that there is no spectral shift of the prompt fluorescence that accompanies the change in temperature of the sample, which is typically observed for the emission from a CT state. Rather, this behaviour is congruent with an emission from an LE state. The seemingly narrower linewidth is an artefact resulting from the normalization and subtraction procedure applied to obtain the prompt fluorescence spectra. We note too that prompt fluorescence is observed upon excitation of the low energy absorption band that we assigned to a CT state. However, the experimentally obtained extinction coefficient for this band is more typical for a state with significant LE character. Based on the coexistence of features that are typical for CT and LE states, we assign the singlet transition to be of a mixed CT/LE character, this assignment is corroborated by the calculations (vide infra).