Synthesis of Homoallylamine Covalent Organic Frameworks Via Hosomi–Sakurai Reaction Under Mild Conditions

Abstract

One-pot multicomponent reactions (MCRs) are a valuable strategy to synthesize functional covalent organic frameworks (COFs) in a single step. Most reported COF syntheses involve solvothermal processes, and because of the harsh reaction conditions, such as high temperature or high pressure, large-scale production of COFs has been limited. The synthesis of homoallylamine substituted COFs via a one-pot Hosomi–Sakurai reaction is reported. At room temperature the reaction of allyltriethylgermane with either terephthalaldehyde or [1,1′-biphenyl]-4,4′-dicarbaldehyde, and 1,3,5-tris(4-aminophenyl)benzene (TAPB) is catalyzed by Sc(OTf)3 to produce two COFs: TAPB-1P-Allyl COF and TAPB-BP-Allyl COF. The allyl functionalized COFs shows high crystallinity, with micropores ranging from 3.2 to 3.9 nm, for TAPB-1P-Allyl COF and TAPB-BP-Allyl COF respectively, and both COFs are hydrolytically stable at different pH levels. Post-synthetic modification of these COFs with iodomethane produces methylated cationic COFs that demonstrates >98% adsorption efficiencies below the detection limit of perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA) from aqueous solutions. After four cycles adsorption efficiency remains high with concentrations of PFOA below the detection limit.