Dye-Doped Polyhedral Oligomeric Silsesquioxane (POSS)-Modified Polymeric Matrices for Highly Efficient and Photostable Solid-State Lasers

Here, the design, synthesis, and characterization of laser nanomaterials based on dye-doped methyl methacrylate (MMA) crosslinked with octa(propyl-methacrylate) polyhedral oligomeric silsesquioxane (8MMAPOSS) is reported in relation to their composition and structure. The influence of the silicon content on the laser action of the dye pyrromethene 567 (PM567) is analyzed in a systematic way by increasing the weight proportion of POSS from 1 to 50%. The influence of the inorganic network structure is studied by replacing the 8MMAPOSS comonomer by both the monofunctionalized heptaisobutyl-methacryl-POSS (1MMAPOSS), which defines the nanostructured linear network with the POSS cages appearing as pendant groups of the polymeric chains, and also by a new 8-hydrogenated POSS incorporated as additive to the polymeric matrices. The new materials exhibit enhanced thermal, optical, and mechanical properties with respect to the pure organic polymers. The organization of the molecular units in these nanomaterials is studied through a structural analysis by solid-state NMR. The domain size of the dispersed phase assures a homogeneous distribution of POSS into the polymer, thus, a continuous phase corresponding to the organic matrix incorporates these nanometer-sized POSS crosslinkers at a molecular level, in agreement with the transparency of the samples. The silicon-oxygen core framework has to be covalently bonded into the polymer backbone instead of being a simple additive and both the silica content and crosslinked degree exhibit a critical influence on the laser action.