Luminescence of solid cyclic polynitramines

The solid form of the cyclic polynitramines known as RDX and HMX have a weak absorption band in the near ultraviolet which is not observed in spectra of the solvated compounds. Fluorescence measurements on solid samples of these materials show a weak emission, the excitation spectrum of which corresponds to this absorption band. Phosphorescence measurements on the solids at 77 K reveal a long-lived emission, the excitation spectrum again corresponding to the weak absorption band. The absorption and the luminescence bands are attributed to charge-transfer self-complex formation in the solid state, and estimates of the energies of the emissive singlet and triplet excited states are given.