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Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

[Image: see text] Self-assembled helical polymers hold great promise as new functional materials, where helical handedness controls useful properties such as circularly polarized light emission or electron spin. The technique of subcomponent self-assembly can generate helical polymers from readily p...

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Autores principales: Greenfield, Jake L., Evans, Emrys W., Di Nuzzo, Daniele, Di Antonio, Marco, Friend, Richard H., Nitschke, Jonathan R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6114842/
https://www.ncbi.nlm.nih.gov/pubmed/30024156
http://dx.doi.org/10.1021/jacs.8b06195
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author Greenfield, Jake L.
Evans, Emrys W.
Di Nuzzo, Daniele
Di Antonio, Marco
Friend, Richard H.
Nitschke, Jonathan R.
author_facet Greenfield, Jake L.
Evans, Emrys W.
Di Nuzzo, Daniele
Di Antonio, Marco
Friend, Richard H.
Nitschke, Jonathan R.
author_sort Greenfield, Jake L.
collection PubMed
description [Image: see text] Self-assembled helical polymers hold great promise as new functional materials, where helical handedness controls useful properties such as circularly polarized light emission or electron spin. The technique of subcomponent self-assembly can generate helical polymers from readily prepared monomers. Here we present three distinct strategies for chiral induction in double-helical metallopolymers prepared via subcomponent self-assembly: (1) employing an enantiopure monomer, (2) polymerization in a chiral solvent, (3) using an enantiopure initiating group. Kinetic and thermodynamic models were developed to describe the polymer growth mechanisms and quantify the strength of chiral induction, respectively. We found the degree of chiral induction to vary as a function of polymer length. Ordered, rod-like aggregates more than 70 nm long were also observed in the solid state. Our findings provide a basis to choose the most suitable method of chiral induction based on length, regiochemical, and stereochemical requirements, allowing stereochemical control to be established in easily accessible ways.
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spelling pubmed-61148422018-08-30 Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers Greenfield, Jake L. Evans, Emrys W. Di Nuzzo, Daniele Di Antonio, Marco Friend, Richard H. Nitschke, Jonathan R. J Am Chem Soc [Image: see text] Self-assembled helical polymers hold great promise as new functional materials, where helical handedness controls useful properties such as circularly polarized light emission or electron spin. The technique of subcomponent self-assembly can generate helical polymers from readily prepared monomers. Here we present three distinct strategies for chiral induction in double-helical metallopolymers prepared via subcomponent self-assembly: (1) employing an enantiopure monomer, (2) polymerization in a chiral solvent, (3) using an enantiopure initiating group. Kinetic and thermodynamic models were developed to describe the polymer growth mechanisms and quantify the strength of chiral induction, respectively. We found the degree of chiral induction to vary as a function of polymer length. Ordered, rod-like aggregates more than 70 nm long were also observed in the solid state. Our findings provide a basis to choose the most suitable method of chiral induction based on length, regiochemical, and stereochemical requirements, allowing stereochemical control to be established in easily accessible ways. American Chemical Society 2018-07-19 2018-08-15 /pmc/articles/PMC6114842/ /pubmed/30024156 http://dx.doi.org/10.1021/jacs.8b06195 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Greenfield, Jake L.
Evans, Emrys W.
Di Nuzzo, Daniele
Di Antonio, Marco
Friend, Richard H.
Nitschke, Jonathan R.
Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title_full Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title_fullStr Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title_full_unstemmed Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title_short Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
title_sort unraveling mechanisms of chiral induction in double-helical metallopolymers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6114842/
https://www.ncbi.nlm.nih.gov/pubmed/30024156
http://dx.doi.org/10.1021/jacs.8b06195
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