Friedel–Crafts reaction of cubic octavinylsilsesquioxane (OVS) and benzene results in a series of hybrid porous polymers (HPPs). The resulting materials, HPP-1 to HPP-4, show relatively high porosity with apparent Brunauer–Emmett–Teller surface areas in a range of 400 m² g⁻¹ to 904 m² g⁻¹, with total pore volumes in the range of 0.24 cm³ g⁻¹ to 0.99 cm³ g⁻¹. Their porosities can be fine tuned by adjusting the mole ratios of OVS and benzene. They feature both micro- and mesopores (HPP-1 and HPP-2) to almost mesopores (HPP-3 and HPP-4) in the networks. The ratios of micropore volume to total pore volume for HPP-1 to HPP-4 were 0.58, 0.42, 0.10, and 0.11, respectively. These materials exhibit comparable surface area and high thermal stability in a N₂ atmosphere. The gas sorption applications reveal that HPP-3 possesses a H₂ uptake of 3.47 mmol g⁻¹ (0.70 wt%) at 77 K and 760 mmHg and a CO₂ uptake of 0.62 mmol g⁻¹ (2.73 wt%) at 298 K and 760 mmHg. These results indicate these materials are promising candidates for storing H₂ and CO₂. In addition, HPP-4 has been successfully postfunctionalized with 3-mercaptopropionic acid via thiol–ene “click” reaction.

Cubic octavinylsilsesquioxane successively reacts with different tetrahedral silicon-centered precursors containing di-, tri-, or tetrabromophenyl groups to prepare hybrid porous polymers (HPPs) via Heck reaction. The resulting materials possess high porosities with Brunauer–Emmett–Teller specific surface areas of up to 875 m² g⁻¹. Their porosities can be tuned by altering the number of the connecting sites of silicon-centered units. For gas storage applications, HPP-5 exhibits the following properties: a high H₂ uptake of 7.76 mmol g⁻¹ (1.56 wt%) at 77 K and 1.01 bar; a moderate CO₂ uptake of 1.04 mmol g⁻¹ (4.58 wt%) at 298 K and 1.04 bar; and a low CH₄ uptake of 0.28 mmol g⁻¹ (0.45 wt%) at 298 K and 1 bar. These results suggest that these polymers can be applied as promising materials for H₂ and CO₂ storage as well as the selective adsorbents of CO₂ rather than CH₄. These polymers are also luminescent with the maximum emission at ca. 420 nm in the solid state; therefore, they could be potentially applied as blue light-emitting materials.