Alternating Copolymerization of Arynes and Aldehydes Enabled by an N-Arylamine Initiator

Here, we report the direct alternating copolymerization of arynes and aldehydes initiated by a simple N-arylamine. The N-arylamine framework is critical for suppressing competing aryne homopolymerization and promotes selective alternating polymerization through a Smiles-type rearrangement pathway. Regeneration of a neutral N-arylamine chain end during each propagation cycle enables complex polymer architectures, including block copolymers and cyclic polymers, through ring-expansion alternating copolymerization. The resulting polymers contain embedded ether linkages that impart an acid-triggered degradability.