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Title: Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly

Abstract

Macrocyclesbased on directional bonding and dynamic covalentbond exchange can be design ed with specificpore shapes, sizes, andfunctionality.These sys- tems retain many of the design criteria and desirableas- pects of two-dimensional (2D) covalent organic frame- works (COFs)but are more easily processed. Here we access discrete hexagonal imine-linked macrocycles by condensing atruncated analogueof1,3,5-tris(4-aminophe- nyl)benzene(TAPB) with terephthaldehyde (PDA). The monomers first condense into polymers buteventually convertinto hexagonal macrocycles in high yield. The high selectivity for hexagonal macrocycles is enforcedby their aggregation and crystallization into layered struc- tures with more sluggish imine exchange. Their formation and exchange processes provide new insight into how imine-linked 2D COF simultaneously polymerize and crys- tallize. Solutions of theseassembled macrocycles were cast into oriented, crystalline films, expanding the poten- tial routes to 2D materials.

Authors:
 [1];  [2];  [2]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [2]
  1. Department of Chemistry, Northwestern University, Evanston Illinois 60208 USA; Department of Chemistry and Chemical Biology, Cornell University, Ithaca New York 14853 USA
  2. Department of Chemistry, Northwestern University, Evanston Illinois 60208 USA
  3. Department of Chemistry, Northwestern University, Evanston Illinois 60208 USA; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne Illinois 60439 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1481752
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 16; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
covalent organic frameworks; dynamic covalent chemistry; imines; self-assembly; supramolecular chemistry

Citation Formats

Chavez, Anton D., Evans, Austin M., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Chen, Lin X., and Dichtel, William R. Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly. United States: N. p., 2018. Web. doi:10.1002/chem.201800459.
Chavez, Anton D., Evans, Austin M., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Chen, Lin X., & Dichtel, William R. Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly. United States. doi:10.1002/chem.201800459.
Chavez, Anton D., Evans, Austin M., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Chen, Lin X., and Dichtel, William R. Mon . "Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly". United States. doi:10.1002/chem.201800459.
@article{osti_1481752,
title = {Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly},
author = {Chavez, Anton D. and Evans, Austin M. and Flanders, Nathan C. and Bisbey, Ryan P. and Vitaku, Edon and Chen, Lin X. and Dichtel, William R.},
abstractNote = {Macrocyclesbased on directional bonding and dynamic covalentbond exchange can be design ed with specificpore shapes, sizes, andfunctionality.These sys- tems retain many of the design criteria and desirableas- pects of two-dimensional (2D) covalent organic frame- works (COFs)but are more easily processed. Here we access discrete hexagonal imine-linked macrocycles by condensing atruncated analogueof1,3,5-tris(4-aminophe- nyl)benzene(TAPB) with terephthaldehyde (PDA). The monomers first condense into polymers buteventually convertinto hexagonal macrocycles in high yield. The high selectivity for hexagonal macrocycles is enforcedby their aggregation and crystallization into layered struc- tures with more sluggish imine exchange. Their formation and exchange processes provide new insight into how imine-linked 2D COF simultaneously polymerize and crys- tallize. Solutions of theseassembled macrocycles were cast into oriented, crystalline films, expanding the poten- tial routes to 2D materials.},
doi = {10.1002/chem.201800459},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 16,
volume = 24,
place = {United States},
year = {2018},
month = {2}
}