Low temperature emission spectra of optically nonlinear N-benzyl-2-methyl-4-nitroaniline crystal

► Temperature dependent fluorescence and phosphorescence spectra of BNA crystal. ► Molecular character of fluorescence in BNA crystal. ► Vibronic structure of fluorescence is attributed to nitro group vibrations. ► Phosphorescence originates from shallow traps depopulated above 30 K. ► Intramolecular charge transfer enhanced by N-benzyl substitution of BNA.