Construction of Porous Aromatic Frameworks with Exceptional Porosity via Building Unit Engineering

The construction of excellent porous organic frameworks (POFs) with high surface areas and stability is always a tremendous challenge in synthetic chemistry. The geometric configuration and reactive group of building unit are crucial factors to influence the structure and porosity of the resulting product. Herein, the design, synthesis, and characterization of two porous aromatic framework (PAF) materials, named PAF‐100 and PAF‐101, are reported via a strategy of building unit engineering. PAF‐100 and PAF‐101 present high Brunauer–Emmett–Teller surface areas exceeding 5000 m2 g−1 and uniform pore size distributions. Furthermore, PAF‐100 and PAF‐101 show high methane uptake with value of 742 and 622 cm3 g−1, respectively, at 298 K and 70 bar. The successful synthesis of PAFs with exceptional porosity from engineered building unit is powerful for constructing highly porous POFs. Building unit engineering to synthesize porous aromatic framework (PAF) material is proposed. PAF‐100 and PAF‐101 with high surface areas exceeding 5000 m2 g−1 are successfully discovered via a dimer‐type molecule as the initial monomer. Furthermore, PAF‐100 and PAF‐101 show high methane uptake thanks to their exceptional porosities. This offers a promising and reliable strategy for the design and synthesis of exceptional porous materials.