Heck coupling reactions are introduced as an efficient method to prepare porous polymers. Novel inorganic-organic hybrid porous polymers (HPPs) were constructed via Heck coupling reactions from cubic functional polyhedral oligomeric silsesquioxanes (POSS), iodinated octaphenylsilsesquioxanes (OPS) and octavinylsilsesquioxanes (OVS) using Pd(OAc)2 /PPh3 as the catalyst. Here, two iodinated OPS were used, IOPS and p-I8 OPS. IOPS was a mixture with 90% octasubstituted OPS (I8 ) and some nonasubstituted OPS (I9 ), while p-I8 OPS was a nearly pure compound with ≥99% I8 and ≥93% para-substitution. IOPS and p-I8 OPS reacted with OVS to produce the porous materials HPP-1 and HPP-2, which exhibited comparable specific surface areas with SBET of 418 ± 20 m(2) g(-1) and 382 ± 20 m(2) g(-1) , respectively, with total pore volumes of 0.28 ± 0.01 cm(3) g(-1) and 0.23 ± 0.01 cm(3) g(-1) , respectively. HPP-1 showed a broader pore size distribution and possessed a more significant contribution from the mesopores, when compared with HPP-2, thereby indicating that IOPS may induce more disorder because of the geometrical asymmetry. HPP-1 and HPP-2 possessed moderate carbon dioxide uptakes of 134 and 124 cm(3) g(-1) at 1 bar at 195 K, making them promising candidates for CO2 capture and storage. The synthesized porous polymers may be easily post-functionalized using the retained ethenylene groups.

Based on the multi-reaction sites of benzene in the Friedel–Crafts reaction with octavinylsilsesquioxane, hybrid polymers with tunable porosity were prepared.

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A series of novel hybrid porous polymers (HPPs), derived from cubic octavinylsilsesquioxane (OVS; [(C2H3SiO1.5)8]) and tetraphenylsilane (TPS), were successfully synthesized through Friedel–Crafts alkylation reaction. The porosities of the HPPs could be tuned by modulating the molar ratio of OVS and TPS. The HPPs showed high porosity, with Brunauer–Emmett–Teller specific surface areas of 518–989 m2 g–1, and total pore volumes of 0.35–0.76 cm3 g–1, as well as narrow pore‐size distributions. For gas sorption application, HPP‐5 possessed a hydrogen uptake of 0.80 wt.‐% at 760 Torr/77 K and a carbon dioxide uptake of 3.31 wt.‐% at 760 Torr/298 K.

Silicones and silicone rubbers are omnipresent in household and industrial products such as lubricants,c oatings, sealants,i nsulators, medicald evices, etc. This plethora of applicationsa rises from their unparalleled properties including hydrophobicity,l ow surfacee nergy,c hemical inertness, extreme temperature stability,e lasticity,a nd biocompatibility.E vent hough silicones have been known for more than five decades, their chemistry is still far from fully understood. Industrially,t he vast majority of processesf or their synthesis, transformation, andu se are based on rather well established, alas outdated technologies, which are frequently empirical and poorly investigated. Thisr eview attempts to summarize the different approaches for the synthesis of silicone rubbers by vulcanizationorc uring of silicone polymers, the catalysts used, and the corresponding reaction mechanisms. Apart from the well-known methods (radical, hydrosilylation, and metal-based condensation), novel approaches such as organo-and bio-catalysis are also addressed.

Hybrid porous polymers derived from cubic octavinylsilsequioxane and planar halogenated benzene monomers exhibit high thermal stability, tunable porosities and potential applications in carbon dioxide storage.

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 Et3 N, P(o-CH3 Ph)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.