Bicyclic Bridge to Improvement: Polymers of intrinsic microporosity are a recently developed class of contorted rigid glassy ladderlike polymers having very high free volume (open internal spaces). The intrinsic porosity of these materials has made them of interest for ultrahigh permeability gas separation membranes. However, while the polymers show good gas permeability, they have only moderate gas selectivity. Carta et al. (p. 303 ; see the Perspective by Guiver and Lee ) hypothesized that if they could replace the dioxin-like rings in their polymers with stiffer bridged bicyclic rings, they could improve the membrane properties of the polymer. By exploiting reactions connected to the formation of Tröger's base to form the multiple covalent bonds needed to make the bicyclic rings, the resulting polymers showed significantly improved selectivity and permeability.

Ultrapermeable benzotriptycene-based PIMs show exceptional gas selectivities that define new positions for the CO ₂ /CH ₄ and CO ₂ /N ₂ Robeson upper bounds.

A highly gas permeable polymer with exceptional size selectivity is prepared by fusing triptycene units together via a poly­merization reaction involving Tröger's base formation. The extreme rigidity of this polymer of intrinsic microporosity (PIM-Trip-TB) facilitates gas permeability data that lie well above the benchmark 2008 Robeson upper bounds for the important O₂/N₂ and H₂/N₂ gas pairs.

The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (<0.7 nm) and large (0.7-1.0 nm) micropores, the former enhancing selectivity and the latter permeability. Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.