Perspectives on the modification of electrodes by polymers of intrinsic microporosity (PIMs) for electroanalysis

Extreme molecular rigidity in the polymer backbone introduces new properties in polymer films or coatings in contact with solution, electrodes, and embedded catalysts. Polymers of intrinsic microporosity (PIMs) with highly rigid molecular structures have initially emerged as gas separation and storage materials. PIMs solution processability and microporosity purely arise from their contorted, molecularly rigid polymer backbone, which pack space inefficiently. In electroanalysis, when applied to electrode surfaces, these microporous materials offer (i) molecular host structures for catalyst immobilisation (for both molecular or nanoparticle catalysts), (ii) stabilisation of host environments (non-capping; i.e . due to molecular rigidity the polymer does not chemisorb onto active sites) for solid nanoparticle materials, (iii) locally enhanced storage of gases/guests with increased apparent activity, (iv) hosts for photocatalysts in photoelectroanalysis, (v) precursors for novel microporous carbons, and (vi) microporous solid-state light emitters for chemi-luminescence (CL) or electrochemiluminescence (ECL) in analysis (with embedded reagents). This perspective reviews some of the recent developments. The range of potential applications of PIMs in electroanalysis is broad and expanding. In the future, customized PIM materials will further add to the molecular toolbox for electroanalytical processes and sensor design.