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Abstract In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents. 

Membrane‐based gas separations are crucial for an energy‐efficient future. However, it is difficult to develop membrane materials that are high‐performing, scalable, and processable. Microporous organic polymers (MOPs) combine benefits for gas sieving and solution processability. Herein, we report membrane performance for a new family of microporous poly(arylene ether)s (PAEs) synthesized via Pd‐catalyzed C−O coupling reactions. The scaffold of these microporous polymers consists of rigid three‐dimensional triptycene and stereocontorted spirobifluorene, endowing these polymers with micropore dimensions attractive for gas separations. This robust PAE synthesis method allows for the facile incorporation of functionalities and branched linkers for control of permeation and mechanical properties. A solution‐processable branched polymer was formed into a submicron film and characterized for permeance and selectivity, revealing lab data that rivals property sets of commercially available membranes already optimized for much thinner configurations. Moreover, the branching motif endows these materials with outstanding plasticization resistance, and their microporous structure and stability enables benefits from competitive sorption, increasing CO₂/CH₄and (H₂S+CO₂)/CH₄selectivity in mixture tests as predicted by the dual‐mode sorption model. The structural tunability, stability, and ease‐of‐processing suggest that this new platform of microporous polymers provides generalizable design strategies to form MOPs at scale for demanding gas separations in industry.

 

Membrane‐based gas separations are crucial for an energy‐efficient future. However, it is difficult to develop membrane materials that are high‐performing, scalable, and processable. Microporous organic polymers (MOPs) combine benefits for gas sieving and solution processability. Herein, we report membrane performance for a new family of microporous poly(arylene ether)s (PAEs) synthesized via Pd‐catalyzed C−O coupling reactions. The scaffold of these microporous polymers consists of rigid three‐dimensional triptycene and stereocontorted spirobifluorene, endowing these polymers with micropore dimensions attractive for gas separations. This robust PAE synthesis method allows for the facile incorporation of functionalities and branched linkers for control of permeation and mechanical properties. A solution‐processable branched polymer was formed into a submicron film and characterized for permeance and selectivity, revealing lab data that rivals property sets of commercially available membranes already optimized for much thinner configurations. Moreover, the branching motif endows these materials with outstanding plasticization resistance, and their microporous structure and stability enables benefits from competitive sorption, increasing CO₂/CH₄and (H₂S+CO₂)/CH₄selectivity in mixture tests as predicted by the dual‐mode sorption model. The structural tunability, stability, and ease‐of‐processing suggest that this new platform of microporous polymers provides generalizable design strategies to form MOPs at scale for demanding gas separations in industry.