Scintillators that exhibit X-ray-excited luminescence have great potential in radiation detection, X-ray imaging, radiotherapy, and non-destructive testing. However, most reported scintillators are limited to inorganic or organic crystal materials, which have some obstacles in repeatability and processability. Here we present a facile strategy to achieve the X-ray-excited organic phosphorescent scintillation from amorphous copolymers through the copolymerization of the bromine-substituted chromophores and acrylic acid. These polymeric scintillators exhibit efficient X-ray responsibility and decent phosphorescent quantum yield up to 51.4% under ambient conditions. The universality of the design principle was further confirmed by a series of copolymers with multi-color radioluminescence ranging from green to orange-red. Moreover, we demonstrated their potential application in X-ray radiography. This finding not only outlines a feasible principle to develop X-ray responsive phosphorescent polymers, but also expands the potential applications of polymer materials with phosphorescence features.

Intermolecular interactions, including attractive and repulsive interactions, play a vital role in manipulating functionalization of the materials from micro to macro dimensions. Despite great success in generation of ultralong organic phosphorescence (UOP) by suppressing non-radiative transitions through attractive interactions recently, there is still no consideration of repulsive interactions on UOP. Herein, we proposed a feasible approach by introducing carboxyl groups into organic phosphors, enabling formation of the intense repulsive interactions between the isolated molecules and the matrix in rigid environment. Our experimental results show a phosphor with a record lifetime and quantum efficiency up to 3.16 s and 50.0% simultaneously in film under ambient conditions. Considering the multiple functions of the flexible films, the potential applications in anti-counterfeiting, afterglow display and visual frequency indicators were demonstrated. This finding not only outlines a fundamental principle to achieve bright organic phosphorescence in film, but also expands the potential applications of UOP materials.