Fluorescence‐Tuned Polyhedral Oligomeric Silsesquioxane‐Based Porous Polymers

Two series of new polyhedral oligomeric silsesquioxane (POSS)‐based fluorescent hybrid porous polymers, HPP‐1 and HPP‐2 , have been prepared by the Heck reaction of octavinylsilsesquioxane with 2,2′,7,7′‐tetrabromo‐9,9′‐spirobifluorene and 1,3,6,8‐tetrabromopyrene, respectively. Three sets of reaction conditions were employed to assess their effect on fluorescence. These materials exhibit tunable fluorescence from nearly no fluorescence to bright fluorescence both in the solid state and dispersed in ethanol under UV light irradiation by simply altering the reaction conditions. We speculated that the difference may be attributable to the fluorescence quenching induced by Et₃N, P(o‐CH₃Ph)₃, and their hydrogen bromide salts employed in the reactions. This finding could give valuable suggestions for the construction of porous polymers with tunable/controllable fluorescence, especially those prepared by Heck and Sonogashira reactions in which these quenchers are used as organic bases or co‐catalysts. In addition, the porosities can also be tuned, but different trends in porosity have been found in these two series of polymers, which suggests that various factors should be carefully considered in the preparation of porous polymers with tunable/controllable porosity. Furthermore, HPP‐1 c showed moderate CO₂ uptake and fluorescence that was efficiently quenched by nitroaromatic explosives, thereby indicating that these materials could be utilized as solid absorbents for the capture and storage of CO₂ and as sensing agents for the detection of explosives.