Single-Crystal One-Dimensional Porous Ladder Covalent Polymers

Abstract

The synthesis of single-crystal, one-dimensional (1D) polymers is of great importance but a formidable challenge. Herein, we report the synthesis of single-crystal 1D ladder polymers in solution by dynamic covalent chemistry. The three-dimensional electron diffraction technique was used to rigorously solve the structure of the crystalline polymers, unveiling that each polymer chain is connected by double covalent bridges and all polymer chains are packed in a staggered and interlaced manner by π−π stacking and hydrogen bonding interactions, making the crystalline polymers highly robust in both thermal and chemical stability. The synthesized single-crystal polymers possess permanent micropores and can efficiently remove CO 2 from the C 2 H 2 /CO 2 mixture to obtain high-purity C 2 H 2 , validated by dynamic breakthrough experiments. This work demonstrates the first example of constructing single-crystal 1D porous ladder polymers with double covalent bridges in solution for efficient C 2 H 2 /CO 2 separation.

Dynamic Entwined Topology in Helical Covalent Polymers Dictated by Competing Supramolecular Interactions

“…Synthesizing samples suitable for these techniques is rare, and only a few comprise 1D polymer chains. [8,17,33,[37][38][39][40] The high conformational freedom of 1D polymers makes organizing the strands within 3D space challenging, so most 1D polymers are amorphous or semi-crystalline. Introducing weaker non-covalent interaction enables a thermodynamic driving force to further organize the polymer strands.…”