Carbon–carbon coupling is a basic design principle for the synthesis of porous organic polymers, which are widely used in gas adsorption/separation, photocatalysis, energy storage, etc. However, the C(sp3)–C(sp3) coupling reaction to construct porous organic polymers remains an important yet elusive objective due to its low reactivity and unknown side reactions. Herein, we report that nickel bis(1,5-cyclooctadiene) (Ni(COD)2), which was a famous catalyst for C(sp2)–C(sp2) coupling reactions, enables highly efficient C(sp3)–C(sp3) homo-coupling reactions to construct porous linear crystalline polymers and flexible three-dimensional porous aromatic frameworks (PAFs) under mild reaction conditions. The resulting linear polymers generated with dibromomethyl arenes have good crystallinity and high melting points (Tm = 286 °C) due to controllability of reaction sites. Furthermore, the PAFs (PAF-64, PAF-65 and PAF-66) stemmed from tri-/tetra-bromomethyl arenes show high surface area (SBET = 390 m2 g−1) and high methane-storage capacity (up to 313 cm3 cm−3) because of their flexible frameworks. This work sheds new light on the construction of novel porous polymers through C(sp3)–C(sp3) coupling reactions and the development of methane-storage materials.
This article is Open Access
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