The enhancement of chain rigidity and gas transport performance of polymers of intrinsic microporosity via intramolecular locking of the spiro-carbon.

Here, we present a new strategy to improve the rigidity of through the introduction of 8-membered ring locking into the flexible spiro-carbon pivot point to produce an interlocked polycyclic structure. This locked version of shows simultaneous increases in both permeability and selectivity that place it well above the Robeson upper bound for a number of important gas pairs. Molecular modelling demonstrates that the locked version of is much more rigid.