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Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles

Supramolecular polymerization of imine-linked macrocycles has been coupled to dynamic imine bond exchange within a series of macrocycles and oligomers. In this way, macrocycle synthesis is driven by supramolecular assembly, either into small aggregates supported by π–π interactions, or high-aspect r...

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Autores principales: Strauss, Michael J., Evans, Austin M., Castano, Ioannina, Li, Rebecca L., Dichtel, William R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148301/
https://www.ncbi.nlm.nih.gov/pubmed/34123290
http://dx.doi.org/10.1039/c9sc05422g
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author Strauss, Michael J.
Evans, Austin M.
Castano, Ioannina
Li, Rebecca L.
Dichtel, William R.
author_facet Strauss, Michael J.
Evans, Austin M.
Castano, Ioannina
Li, Rebecca L.
Dichtel, William R.
author_sort Strauss, Michael J.
collection PubMed
description Supramolecular polymerization of imine-linked macrocycles has been coupled to dynamic imine bond exchange within a series of macrocycles and oligomers. In this way, macrocycle synthesis is driven by supramolecular assembly, either into small aggregates supported by π–π interactions, or high-aspect ratio nanotubes stabilized primarily by electrostatic and solvophobic interactions. For the latter, supramolecular polymerization into nanotubes restricts imine exchange, thereby conferring chemical stability to the assemblies and their constituent macrocycles. Competition in the formation and component exchange among macrocycles favored pyridine-2,6-diimine-linked species due to their rapid synthesis, thermodynamic stability, and assembly into high-aspect ratio nanotubes under the reaction conditions. In addition, the pyridine-containing nanotubes inhibit the formation of similar macrocycles containing benzene-1,3-diimine-linkages, presumably by disrupting their assembly and templation. Finally, we exploit rapid imine exchange within weak, low-aspect ratio macrocycle aggregates to carry out monomer exchange reactions to macrocycles bearing pyridine moieties. Once a pyridine-containing dialdehyde has exchanged into a macrocycle, the macrocycle becomes capable of nanotube formation, which dramatically slows further imine exchange. This kinetic trap provides chemically diverse macrocycles that are not attainable by direct synthetic methods. Together these findings provide new insights into coupling supramolecular polymerization and dynamic covalent bond-forming processes and leverages this insight to target asymmetric nanotubes. We envision these findings spurring further research efforts in the synthesis of nanostructures with designed and emergent properties.
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spelling pubmed-81483012021-06-11 Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles Strauss, Michael J. Evans, Austin M. Castano, Ioannina Li, Rebecca L. Dichtel, William R. Chem Sci Chemistry Supramolecular polymerization of imine-linked macrocycles has been coupled to dynamic imine bond exchange within a series of macrocycles and oligomers. In this way, macrocycle synthesis is driven by supramolecular assembly, either into small aggregates supported by π–π interactions, or high-aspect ratio nanotubes stabilized primarily by electrostatic and solvophobic interactions. For the latter, supramolecular polymerization into nanotubes restricts imine exchange, thereby conferring chemical stability to the assemblies and their constituent macrocycles. Competition in the formation and component exchange among macrocycles favored pyridine-2,6-diimine-linked species due to their rapid synthesis, thermodynamic stability, and assembly into high-aspect ratio nanotubes under the reaction conditions. In addition, the pyridine-containing nanotubes inhibit the formation of similar macrocycles containing benzene-1,3-diimine-linkages, presumably by disrupting their assembly and templation. Finally, we exploit rapid imine exchange within weak, low-aspect ratio macrocycle aggregates to carry out monomer exchange reactions to macrocycles bearing pyridine moieties. Once a pyridine-containing dialdehyde has exchanged into a macrocycle, the macrocycle becomes capable of nanotube formation, which dramatically slows further imine exchange. This kinetic trap provides chemically diverse macrocycles that are not attainable by direct synthetic methods. Together these findings provide new insights into coupling supramolecular polymerization and dynamic covalent bond-forming processes and leverages this insight to target asymmetric nanotubes. We envision these findings spurring further research efforts in the synthesis of nanostructures with designed and emergent properties. The Royal Society of Chemistry 2020-01-09 /pmc/articles/PMC8148301/ /pubmed/34123290 http://dx.doi.org/10.1039/c9sc05422g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Strauss, Michael J.
Evans, Austin M.
Castano, Ioannina
Li, Rebecca L.
Dichtel, William R.
Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title_full Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title_fullStr Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title_full_unstemmed Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title_short Supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
title_sort supramolecular polymerization provides non-equilibrium product distributions of imine-linked macrocycles
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148301/
https://www.ncbi.nlm.nih.gov/pubmed/34123290
http://dx.doi.org/10.1039/c9sc05422g
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