Metallo‐Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination

In this study, we established a feasible strategy to construct a new type of metallo‐polymer with helicoidal structure through the combination of covalent polymerization and intramolecular coordination‐driven self‐assembly. In the design, a tetratopic monomer (M) was prepared with two terminal alkynes in the outer rim for polymerization, and two terpyridines (TPYs) in the inner rim for subsequent folding by selective intramolecular coordination. Then, the linear covalent polymer (P) was synthesized by polymerization of M via Glaser‐Hay homocoupling reaction. Finally, intramolecular coordination interactions between TPYs and Zn(II) folded the backbone of P into a right‐ or left‐handed metallo‐helicoid (H) with double rims. Owing to multiple positive charges on the inner rim of helicoid, double‐stranded DNA molecules (dsDNA) could interact with H through electrostatic interactions. Remarkably, dsDNA allowed exclusive formation of H with right handedness by means of chiral induction. A new type of metallo‐polymer with helicoidal structure was constructed through the combination of covalent polymerization and intramolecular coordination‐driven self‐assembly. Owing to the positive charges on the inner rim of helicoid, double‐stranded DNA molecules (dsDNA) could interact with metallo‐helicoid (H) via electrostatic interactions. Notably, dsDNA allowed exclusive formation of H with right handedness by means of chiral induction.