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Living supramolecular polymerization of fluorinated cyclohexanes

The development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem...

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Autores principales: Shyshov, Oleksandr, Haridas, Shyamkumar Vadakket, Pesce, Luca, Qi, Haoyuan, Gardin, Andrea, Bochicchio, Davide, Kaiser, Ute, Pavan, Giovanni M., von Delius, Max
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8149861/
https://www.ncbi.nlm.nih.gov/pubmed/34035277
http://dx.doi.org/10.1038/s41467-021-23370-y
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author Shyshov, Oleksandr
Haridas, Shyamkumar Vadakket
Pesce, Luca
Qi, Haoyuan
Gardin, Andrea
Bochicchio, Davide
Kaiser, Ute
Pavan, Giovanni M.
von Delius, Max
author_facet Shyshov, Oleksandr
Haridas, Shyamkumar Vadakket
Pesce, Luca
Qi, Haoyuan
Gardin, Andrea
Bochicchio, Davide
Kaiser, Ute
Pavan, Giovanni M.
von Delius, Max
author_sort Shyshov, Oleksandr
collection PubMed
description The development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach.
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spelling pubmed-81498612021-06-11 Living supramolecular polymerization of fluorinated cyclohexanes Shyshov, Oleksandr Haridas, Shyamkumar Vadakket Pesce, Luca Qi, Haoyuan Gardin, Andrea Bochicchio, Davide Kaiser, Ute Pavan, Giovanni M. von Delius, Max Nat Commun Article The development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach. Nature Publishing Group UK 2021-05-25 /pmc/articles/PMC8149861/ /pubmed/34035277 http://dx.doi.org/10.1038/s41467-021-23370-y Text en © The Author(s) 2021, corrected publication 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Shyshov, Oleksandr
Haridas, Shyamkumar Vadakket
Pesce, Luca
Qi, Haoyuan
Gardin, Andrea
Bochicchio, Davide
Kaiser, Ute
Pavan, Giovanni M.
von Delius, Max
Living supramolecular polymerization of fluorinated cyclohexanes
title Living supramolecular polymerization of fluorinated cyclohexanes
title_full Living supramolecular polymerization of fluorinated cyclohexanes
title_fullStr Living supramolecular polymerization of fluorinated cyclohexanes
title_full_unstemmed Living supramolecular polymerization of fluorinated cyclohexanes
title_short Living supramolecular polymerization of fluorinated cyclohexanes
title_sort living supramolecular polymerization of fluorinated cyclohexanes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8149861/
https://www.ncbi.nlm.nih.gov/pubmed/34035277
http://dx.doi.org/10.1038/s41467-021-23370-y
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