Nickel-catalyzed synthesis of nanoporous organic frameworks and their potential use in gas storage applications

The synthesis of highly nanoporous organic frameworks (NPOFs) has been established using nickel(0)-catalyzed Yamamoto coupling reactions, which has afforded highly porous polymers featuring remarkable chemical and thermal stability. Treatment of 1,3,5-tris(4-bromophenyl)benzene, 1,2,4,5-tetrakis(4-bromophenyl)benzene, or 1,3,5,7-tetrakis(4-iodophenyl)adamantane with Ni(cod)₂ in DMF at 80°C for 48 h afforded the nanoporous organic frameworks, NPOF-1, NPOF-2, and NPOF-3, respectively, as white powders in quantitative yields. All NPOFs are insoluble in common organic solvents such as dimethylformamide, tetrahydrofuran, toluene, dichloromethane, and methanol. The chemical composition and structural aspects of NPOFs were investigated by spectral and analytical methods while porosity was examined by nitrogen porosity measurements. In spite of their amorphous nature, NPOFs exhibit permanent porosity and high Langmuir surface areas (NPOF-1: 2,635 m² g^?1; NPOF-2: 4,227 m² g^?1; NPOF-3: 2,423 m² g^?1), which make them attractive for subsequent use in gas storage and separation applications, among others. The performance of NPOFs in hydrogen storage was evaluated at 1 bar and 77 K and revealed that these highly porous architectures can store up to 1.45 wt% of hydrogen.