Synthesis and Gas Adsorption Properties of Tetra‐Armed Microporous Organic Polymer Networks Based on Triphenylamine

Two novel tetra‐armed microporous organic polymers have been designed and synthesized via a nickel‐catalyzed Yamamoto‐type Ullmann cross‐coupling reaction or Suzuki cross‐coupling polycondensation. These polymers are stable in various solvents, including concentrated hydrochloric acid, and are thermally stable. The homocoupled polymer YPTPA shows much higher Brunauer–Emmet–Teller‐specific surface area up to 1557 m² g⁻¹ than the copolymer SPTPA (544 m² g⁻¹), and a high CO₂ uptake ability of 3.03 mmol g⁻¹ (1.13 bar/273 K) with a CO₂/N₂ sorption selectivity of 17.3:1. Both polymers show high isosteric heats of CO₂ adsorption (22.7–26.5 kJ mol⁻¹) because the incorporation of nitrogen atoms into the skeleton of microporous organic polymers enhances the interaction between the pore wall and the CO₂ molecules. The values are higher than those of the porous aromatic frameworks, which contain neither additional polar functional groups nor nitrogen atoms, and are rather close to those of previously reported microporous organic polymers containing the nitrogen atoms on the pore wall. These data show that these materials would be potential candidates for applications in post‐combustion CO₂ capture and sequestration technology.