Ferrocene metallopolymers of intrinsic microporosity (MPIMs).

We show here that non-network metallopolymers can possess intrinsic microporosity stemming from contortion introduced by metallocene building blocks. Metallopolymers constructed from ferrocenyl building blocks linked by phenyldiacetylene bridges are synthesized and possess BET surface areas up to 400 m2 g-1. As solubility imparted by pendant groups reduces porosity, copolymerization is used to simultaneously improve both accessible surface area and solubility. Spectroscopic analysis provides evidence that mixed valency between neighboring ferrocenyl units is supported in these polymers.