Metal-Free Multicomponent Tandem Polymerizations of Alkynes, Amines, and Formaldehyde toward Structure- and Sequence-Controlled Luminescent Polyheterocycles.

Sequence-controlled polymers, including biopolymers such as DNA, RNA, and proteins, have attracted much attention recently because of their sequence-dependent functionalities. The development of an efficient synthetic approach for non-natural sequence-controlled polymers is hence of great importance. Multicomponent polymerizations (MCPs) as a powerful and popular synthetic approach for functional polymers with great structural diversity have been demonstrated to be a promising tool for the synthesis of sequence-controlled polymers. In this work, we developed a facile metal-free one-pot multicomponent tandem polymerization (MCTP) of activated internal alkynes, aromatic diamines, and formaldehyde to successfully synthesize structural-regulated and sequence-controlled polyheterocycles with high molecular weights (up to 69 800 g/mol) in high yields (up to 99%). Through such MCTP, polymers with the in situ generated multisubstituted tetrahydropyrimidines or dihydropyrrolones in the backbone and inherent luminescence can be easily obtained with high atom economy and environmental benefit, which is inaccessible by other synthetic approaches.