A Versatile Method for the End-Functionalization of Polycarbenes.

End-functionalization is an effective strategy for constructing functional materials. A method for chain-end functionalization of helical polycarbenes is herein developed that relied on Sonogashira coupling reaction. In this work, a family of helical polycarbenes with controlled molecular mass (Mn ) and low polydispersity (Mw /Mn ) is readily prepared using Pd(II) and the Wei-Phos ligand as initiator. The Pd(II) complex is confirmed to remain at the chain end of polycarbene. Subsequently, a series of terminal alkyne derivatives with interesting functional groups, including the F atom, aldehyde, or anthracene groups, are synthesized. They could be installed at the chain end of polycarbene through Sonogashira coupling reaction catalyzed by the Pd(II) complex at the chain end. Moreover, a couple of hybrid block copolymers are easily obtained by installing terminal alkynes modified by another type of polymer. The structures of the isolated polymers are confirmed by 1 H nuclear magnetic resonance (1 H NMR), 19 F nuclear magnetic resonance (19 F NMR), 31 P nuclear magnetic resonance (31 P NMR), and Fourier transform infrared spectroscopy (FT-IR), respectively. The self-assembly properties of the hybrid block copolymers are also investigated by atomic force spectroscopy analysis. By the hereby developed method, various functional groups can be introduced at the chain end of helical polycarbenes for constructing functional polymer materials, moreover, the transition metal residues at the end of polymer chains can be easily removed.