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Abstract

Imidazolium based porous cationic polymers were synthesized using an innovative and facile approach, which takes advantage of the Debus-Radziszewski reaction to obtain meso-/microporous polymers following click-chemistry principles. In the obtained set of materials, click based-porous cationic polymers have the same cationic backbone whereas they bear the commonly used anions of imidazolium poly(ionic liquid)s. These materials show hierarchical porosity and good specific surface area. Furthermore, their chemical structure was extensively characterized using ATR-FTIR and SS-NMR spectroscopies, and HR-MS. These polymers show good performance towards carbon dioxide sorption, especially those possessing the acetate anion. This polymer can uptake 2 mmol/g of CO2 at 1 bar and 273 K, a value which is among the highest recorded for imidazolium poly(ionic liquid)s. These polymers were also modified in order to introduce N-heterocyclic carbene along the backbone. Carbon dioxide loading in the carbene containing polymer is in the same range of the non-modified versions, but the nature of the interaction is substantially different. Combined use of in-situ FTIR spectroscopy and micro-calorimetry evidenced a chemisorption phenomenon that brings to the formation of an imidazolium carboxylate zwitterion.