Barbier-Type Nitro/Nitroso Addition Polymerization as a Versatile Approach for Molecular Design of Polyarylamines through C–N Bond Formation

The doping of a polymer chain with nitrogen is an efficient strategy to endow polymer materials with functionality. However, the molecular design of polyarylamines through direct C–N bond formation is still challenging. Herein, a novel polymerization method, named Barbier-type nitro/nitroso addition polymerization, is reported as a versatile approach for molecular design of polyarylamines through C–N bond formation, by utilizing electrophilic nitro/nitroso groups as polymerizable groups. Through Barbier-type nitro/nitroso addition polymerization, a series of polyarylamines have been prepared, including ortho-polyaniline, para-polyaniline, meta-polyaniline, para-polymethylaniline, and polynaphthylamine, most of which are hard to be synthesized by current other polymerization methods. By introducing the Barbier-type nitro/nitroso addition into polymer chemistry, the polymerization methodology, monomer, and polymer libraries of polymer chemistry are expanded and a novel avenue is opened up for molecular design of nitrogen-containing polymer materials through direct formation of a C–N bond.