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Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles’ intrinsic host-guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a porous organic polymer through the condensation reaction between cyclotetrabenzil with 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 oC. Notably, following the condensation reaction, the macrocycle favors 3D growth rather than 2D one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with the BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide /nitrogen mixtures.

Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity