Click Assembly of Dye-Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems

摘要

New hybrid organic–inorganic\uddyes based on an azide-functionalized\udcubic octasilsesquioxane (POSS)\udas the inorganic part and a 4,4-difluoro-\ud4-bora-3a,4a-diaza-s-indacene\ud(BDP) chromophore as the organic\udcomponent have been synthesized by\udcopper(I)-catalyzed 1,3-dipolar cycloaddition\udof azides to alkynes. We have\udstudied the effects of the linkage group\udof BDP to the POSS unit and the\uddegree of functionalization of this inorganic\udcore on the ensuing optical properties\udby comparison with model dyes.\udThe high fluorescence of the BDP dye\udis preserved in spite of the linked chain\udat its meso position, even after attaching\udone BDP moiety to the POSS core.\udThe laser action of the new dyes has\udbeen analyzed under transversal pumping\udat 532 nm in both the liquid phase\udand when incorporated into solid polymeric\udmatrices. The monosubstituted\udnew hybrid dye exhibits high lasing efficiency\udof up to 56% with high photostability,\udwith its laser output remaining\udat the initial value after 4 105 pump\udpulses in the same position of the\udsample at a repetition rate of 30 Hz.\udHowever, functionalization of the\udPOSS core with eight fluorophores\udleads to dye aggregation, as quantum\udmechanical simulation has revealed,\udworsening the optical properties and\udextinguishing the laser action. The new\udhybrid systems based on dye-linked\udPOSS nanoparticles open up the possibility\udof using these new photonic materials\udas alternative sources for optoelectronic\uddevices, competing with\uddendronized or grafted polymers