Dual Trapping of a Metastable Planarized Triarylborane π-System Based on Folding and Lewis Acid-Base Complexation for Seeded Polymerization.

Abstract

We report the kinetically controlled supramolecular polymerization of boron-containing π-conjugated molecules, which was enabled by a seeding method based on dual trapping of a metastable state by synergistic intramolecular hydrogen bonding and Lewis acid-based complexation. Planarized triarylborane-based 1, which bears a diamide chain with chiral alkyl groups, was synthesized. Upon cooling, the solution of monomer 1 afforded a supramolecular polymerization in a cooperative manner to form helical supramolecular nanostructures with intense J-type aggregate emission. In the presence of pyridine, the triarylborane moiety formed a Lewis acid-base complex, which enhances the stabilization of the metastable monomeric state. An assembly incompetent structure with a folded diamide chain conformation and a pyridine moiety axially coordinated to the boron atom is responsible for slowing the spontaneous aggregation. The seeding method was successfully applied to the solution to produce homogeneous nanofibers even at a high (millimolar-level) concentration. This unprecedented kinetic control via dual trapping provides an effective method to achieve seed-initiated polymerization under concentrated conditions.