“…[8][9][10][11][12] Among oligomeric siloxane units, the cubic octameric siloxane cage Si 8 O 12 , commonly termed double four-ring (D4R), is of particular interest as an ideal molecular building unit because of its rigidity, hyperbranched architecture, high symmetry, and ease of functionalization. [13] D4R moieties bearing specific functional groups such as aldehyde, carboxyl, and epoxy have been used in diverse forms as model catalysts, components for polymer blends, organic light-emitting diodes, and so on. [14] Early attempts to construct silicabased micro-and/or mesoporous materials with molecular Abstract: Sonogashira cross-coupling of bromophenylethenyl-terminated cubic, double four-ring, siloxane cages with di-/triethynyl compounds results in microporous poly(ethynylene ary-A C H T U N G T R E N N U N G leneethenylene silsesquioxane) networks, simply termed as polyorganosiloxane networks (PSNs).…”