We have developed a series of porous, linear metallopolymers termed “metallopolymers of intrinsic microporosity” (MPIMs). Introduced metal ions in these non-network metallopolymers enable the polymers to exhibit intrinsic microporosity stemming from the backbone contortion. MPIMs consisting of ferrocenyl building blocks linked by phenyldiacetylene units possess BET surface areas up to 400 m<sup>2</sup>/g. Computational modeling is consistent with our prediction that porosity increases with the polymer’s degree of polymerization. Due to the conjugated structure of MPIMs, electronic communication between bridged ferrocenes should be supported. Spectroscopic analysis provides evidence for mixed valency between neighboring ferrocenyl units. Some property measurements were limited by the poor solubility of this class of MPIMs, so copolymers with pendant groups affixed to the phenyldiacetylene units were synthesized to simultaneously improve both porosity and solubility. We now describe efforts to obtain pure oligomers of precise degrees of polymerization, which are expected to have even better solubility compared the analogous with high MW MPIMs. Further exploration of optical and electronic properties will provide a better understanding of polymer characteristics and allow us to precisely compare the differences in properties between monomers, short oligomers, long oligomers, and polymers.

Ferrocene metallopolymers of intrinsic microporosity (MPIMs)

ACS Spring 2022

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