Porous organic polymers (POPs) have gained tremendous attention owing to their chemical tunability, stability and high surface areas. Whereas there are several examples of fully conjugated two-dimensional (2D) POPs, three-dimensional (3D) ones are rather challenging to realize in the absence of structural templates. Herein, we report the base-catalyzed direct synthesis of a fully conjugated 3D POPs, named benzyne-derived polymers (BDPs), containing biphenylene and tetraphenylene moieties starting from a simple bisbenzyne precursor, which undergoes [2+2] and [2+2+2+2] cycloaddition reactions to form BDPs primarily composed of biphenylene and tetraphenylene moieties. The resulting polymers exhibited ultramicroporous structures with surface areas up to 544 m2 g-1 and very high CO2 /N2 selectivities.
Keywords: benzyne derived polymers; cycloaddition polymerization; gas uptake; porous materials; self-polymerization.
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.