Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions
This work presents the first transition metal-free synthesis of oxygen-linked aromatic polymers by integrating iterative exponential polymer growth (IEG) with nucleophilic aromatic substitution (SNAr) reactions. Our approach applies methyl sulfones as the leaving groups, which eliminate the need for...
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doaj-54d5f6dd58f64d3dbc7852b28719d3952021-04-28T05:53:57ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462021-04-01910.3389/fchem.2021.620017620017Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution ReactionsTyler J. Jaynes0Mona Sharafi1Joseph P. Campbell2Jessica Bocanegra3Kyle T. McKay4Kassondra Little5Reilly Osadchey Brown6Danielle L. Gray7Toby J. Woods8Jianing Li9Severin T. Schneebeli10Department of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesGeorge L. Clark X-Ray Facility and 3M Materials Laboratory, University of Illinois at Urbana-Champaign, Urbana, IL, United StatesGeorge L. Clark X-Ray Facility and 3M Materials Laboratory, University of Illinois at Urbana-Champaign, Urbana, IL, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesDepartment of Chemistry, University of Vermont, Burlington, VT, United StatesThis work presents the first transition metal-free synthesis of oxygen-linked aromatic polymers by integrating iterative exponential polymer growth (IEG) with nucleophilic aromatic substitution (SNAr) reactions. Our approach applies methyl sulfones as the leaving groups, which eliminate the need for a transition metal catalyst, while also providing flexibility in functionality and configuration of the building blocks used. As indicated by 1) 1H-1H NOESY NMR spectroscopy, 2) single-crystal X-ray crystallography, and 3) density functional theory (DFT) calculations, the unimolecular polymers obtained are folded by nonclassical hydrogen bonds formed between the oxygens of the electron-rich aromatic rings and the positively polarized C–H bonds of the electron-poor pyrimidine functions. Our results not only introduce a transition metal-free synthetic methodology to access precision polymers but also demonstrate how interactions between relatively small, neutral aromatic units in the polymers can be utilized as new supramolecular interaction pairs to control the folding of precision macromolecules.https://www.frontiersin.org/articles/10.3389/fchem.2021.620017/fulliterative convergent/divergent polymer synthesisSNAr reactionsnonclassical hydrogen bondingnuclear magnetic resonance spectroscopypolymer foldingiterative exponential polymer growth |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Tyler J. Jaynes Mona Sharafi Joseph P. Campbell Jessica Bocanegra Kyle T. McKay Kassondra Little Reilly Osadchey Brown Danielle L. Gray Toby J. Woods Jianing Li Severin T. Schneebeli |
spellingShingle |
Tyler J. Jaynes Mona Sharafi Joseph P. Campbell Jessica Bocanegra Kyle T. McKay Kassondra Little Reilly Osadchey Brown Danielle L. Gray Toby J. Woods Jianing Li Severin T. Schneebeli Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions Frontiers in Chemistry iterative convergent/divergent polymer synthesis SNAr reactions nonclassical hydrogen bonding nuclear magnetic resonance spectroscopy polymer folding iterative exponential polymer growth |
author_facet |
Tyler J. Jaynes Mona Sharafi Joseph P. Campbell Jessica Bocanegra Kyle T. McKay Kassondra Little Reilly Osadchey Brown Danielle L. Gray Toby J. Woods Jianing Li Severin T. Schneebeli |
author_sort |
Tyler J. Jaynes |
title |
Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions |
title_short |
Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions |
title_full |
Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions |
title_fullStr |
Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions |
title_full_unstemmed |
Iterative Exponential Growth of Oxygen-Linked Aromatic Polymers Driven by Nucleophilic Aromatic Substitution Reactions |
title_sort |
iterative exponential growth of oxygen-linked aromatic polymers driven by nucleophilic aromatic substitution reactions |
publisher |
Frontiers Media S.A. |
series |
Frontiers in Chemistry |
issn |
2296-2646 |
publishDate |
2021-04-01 |
description |
This work presents the first transition metal-free synthesis of oxygen-linked aromatic polymers by integrating iterative exponential polymer growth (IEG) with nucleophilic aromatic substitution (SNAr) reactions. Our approach applies methyl sulfones as the leaving groups, which eliminate the need for a transition metal catalyst, while also providing flexibility in functionality and configuration of the building blocks used. As indicated by 1) 1H-1H NOESY NMR spectroscopy, 2) single-crystal X-ray crystallography, and 3) density functional theory (DFT) calculations, the unimolecular polymers obtained are folded by nonclassical hydrogen bonds formed between the oxygens of the electron-rich aromatic rings and the positively polarized C–H bonds of the electron-poor pyrimidine functions. Our results not only introduce a transition metal-free synthetic methodology to access precision polymers but also demonstrate how interactions between relatively small, neutral aromatic units in the polymers can be utilized as new supramolecular interaction pairs to control the folding of precision macromolecules. |
topic |
iterative convergent/divergent polymer synthesis SNAr reactions nonclassical hydrogen bonding nuclear magnetic resonance spectroscopy polymer folding iterative exponential polymer growth |
url |
https://www.frontiersin.org/articles/10.3389/fchem.2021.620017/full |
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