This tutorial review describes recent research directed towards the synthesis of polymer-based organic microporous materials termed Polymers of Intrinsic Microporosity (PIMs). PIMs can be prepared either as insoluble networks or soluble polymers with both types giving solids that exhibit analogous behaviour to that of conventional microporous materials such as activated carbons. Soluble PIMs may be processed into thin films for use as highly selective gas separation membranes. Preliminary results also demonstrate the potential of PIMs for heterogeneous catalysis and hydrogen storage.

Microporous materials can be derived directly from soluble polymers whose randomly contorted shapes prevent an efficient packing of the macromolecules in the solid state.

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.