Equilibration of Imine‐Linked Polymers to Hexagonal Macrocycles Driven by Self‐Assembly
Abstract
Macrocycles based on directional bonding and dynamic covalent bond exchange can be designed with specific pore shapes, sizes, and functionality. These systems retain many of the design criteria and desirable aspects of two‐dimensional (2D) covalent organic frameworks (COFs) but are more easily processed. Here we access discrete hexagonal imine‐linked macrocycles by condensing a truncated analogue of 1,3,5‐tris(4‐aminophenyl)benzene (TAPB) with terephthaldehyde (PDA). The monomers first condense into polymers but eventually convert into hexagonal macrocycles in high yield. The high selectivity for hexagonal macrocycles is enforced by their aggregation and crystallization into layered structures with more sluggish imine exchange. Their formation and exchange processes provide new insight into how imine‐linked 2D COF simultaneously polymerize and crystallize. Solutions of these assembled macrocycles were cast into oriented, crystalline films, expanding the potential routes to 2D materials.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Feb 26, 2018
- Source ID
- 10.1002/chem.201800459
Entities
People
- Anton D. Chavez
- Austin M Evans
- Edon Vitaku
- Lin Chen
- Nathan C Flanders
- Ryan P Bisbey
- William Dichtel
Organizations
- Argonne National Laboratory
- Army Research Office
- Cornell University
- National Science Foundation
- Northwestern University
- Office of Basic Energy Sciences
- United States Department of Energy