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

Guang‐Qiang Yin, Sneha Kandapal, Chung‐Hao Liu, Heng Wang, Jianxiang Huang, Shuting Jiang, Ji Tan, Yu Yan, Sandra Khalife, Ruhong Zhou, Libin Ye, Bingqian Xu, Hai‐Bo Yang, Mu‐Ping Nieh, Xiaopeng Li

2020Angewandte Chemie International Edition25 citationsDOI

Abstract

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.

Topics & Concepts

Intramolecular forcePolymerizationChemistryFolding (DSP implementation)Covalent bondCrystallographyMoleculePolymerStereochemistryOrganic chemistryEngineeringElectrical engineeringCovalent Organic Framework ApplicationsLuminescence and Fluorescent MaterialsSynthesis and Properties of Aromatic Compounds