“…Polyhedral oligomeric silsesquioxanes (POSS, (R-SiO 1.5 ) n , n = 6, 8, 10, 12, etc. ), are one class of nanosized hybrid nanoblocks of interest in many research areas, including self-organized system-related materials, − polymer nanocomposites, − and inorganic–organic hybrid functional coatings. − With the rigid three-dimensional (3D) configuration, high reactivity, and hybrid nature, , in particular, an intriguing feature of similarity to the secondary building units of zeolites, POSS have also been considered as ideal nanoblocks to develop advanced HPPs. ,− To date, many studies on the geometry effect of aromatic linking units, such as linear-, planar-, tetrahedral-, propeller-, and ladder-like units, ,,− have revealed that the topological combination of POSS with these linking units can tune the porosity and yield various POSS-based porous materials (PPMs) with high performance. However, most studies on PPMs focused on T 8 POSS, and studies on the geometry effect of larger POSS such as T 10 , T 12 , and other compounds are limited (Figure a).…”