@article{989b60805fc84aca9a08f16d193403e1,
title = "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.",
keywords = "covalent organic frameworks, dynamic covalent chemistry, imines, self-assembly, supramolecular chemistry",
author = "Chavez, {Anton D.} and Evans, {Austin M.} and Flanders, {Nathan C.} and Bisbey, {Ryan P.} and Edon Vitaku and Chen, {Lin X.} and Dichtel, {William R.}",
note = "Funding Information: This work was funded by the Army Research Office through the Multidisciplinary University Research Initiative (MURI, W911NF-15-1-0447, to W.R.D.). A.D.C. was supported through a National Defense Science and Engineering Graduate Fellowship (NDSEG). This work made use of the Integrated Molecular Structure Education and Research Center (IMSERC) at North-western University, which has received support from the National Science Foundation (NSF; (CHE-1048773), the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and the International Insti- tute for Nanotechnology (IIN). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. N.C.F is partially supported by Basic Energy Science, CBG Division, US Department of Energy and resources at the Advanced Photon Source were funded by the National Science Foundation under Award Number 0960140. A.M.E. is supported by the National Science Foundation Graduate Research Fellowship (DGE-1324585), and North-western University and the International Institute for Nanotechnology via a Ryan Fellowship. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",
year = "2018",
month = mar,
day = "15",
doi = "10.1002/chem.201800459",
language = "English (US)",
volume = "24",
pages = "3989--3993",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "16",
}