Luminescence properties of 1,8-naphthalimide derivatives in solution, in their crystals, and in co-crystals: Toward room-temperature phosphorescence from organic materials

Crystalline 1,8-naphthalimide derivatives bearing a bromine atom at the 4-position and a 2-, 3-, or 4- methylpyridine at the imidic N-position have been synthesized, and their co-crystals with the coformer 1,4- diiodotetrafluorobenzene have been obtained via mechanochemistry. The structure of crystals and co-crystals has been characterized by means of X-ray diffraction and Raman and IR analysis. The luminescence properties of the derivatives have been explored both in solution and in their solid crystals and co-crystals. All of the compounds exhibit weak fluorescence in air-equilibrated solutions at room temperature and both fluorescence and phosphorescence at low temperature. In air-free solvent, all of the derivatives show phosphorescence at room temperature, at variance with the unsubstituted 1,8-naphthalimide model. Solid crystals display a red-shifted fluorescence with an increased emission quantum yield as compared to solution, whereas co-crystals show different behaviors. For all of the solid compounds, phosphorescence could be observed at room temperature by means of a gated detection. The dependence of the luminescence features of the solid materials on the intermolecular interactions that occur in the lattice is discussed. © 2014 American Chemical Society.