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Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

Jake L. Greenfield, Emrys Evans Orcid Logo, Daniele Di Nuzzo, Marco Di Antonio, Richard H. Friend, Jonathan R. Nitschke

Journal of the American Chemical Society, Volume: 140, Issue: 32, Pages: 10344 - 10353

Swansea University Author: Emrys Evans Orcid Logo

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DOI (Published version): 10.1021/jacs.8b06195

Abstract

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....

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Published in: Journal of the American Chemical Society
ISSN: 0002-7863 1520-5126
Published: American Chemical Society (ACS) 2018
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URI: https://cronfa.swan.ac.uk/Record/cronfa57571
first_indexed 2021-08-10T08:28:12Z
last_indexed 2021-09-09T03:21:01Z
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spelling 2021-09-08T15:48:38.7222646 v2 57571 2021-08-10 Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers 538e217307dac24c9642ef1b03b41485 0000-0002-9092-3938 Emrys Evans Emrys Evans true false 2021-08-10 EAAS 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. Journal Article Journal of the American Chemical Society 140 32 10344 10353 American Chemical Society (ACS) 0002-7863 1520-5126 15 8 2018 2018-08-15 10.1021/jacs.8b06195 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University External research funder(s) paid the OA fee (includes OA grants disbursed by the Library) This work was funded by the UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1 and EP/M01083x/1) and the European Research Council (ERC 695009). 2021-09-08T15:48:38.7222646 2021-08-10T09:28:02.6797526 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Jake L. Greenfield 1 Emrys Evans 0000-0002-9092-3938 2 Daniele Di Nuzzo 3 Marco Di Antonio 4 Richard H. Friend 5 Jonathan R. Nitschke 6 57571__20787__e2eada12b7b04defa90b559c3ff791d4.pdf 57571.pdf 2021-09-08T15:47:44.5436730 Output 3509035 application/pdf Version of Record true This is an open access article published under a Creative Commons Attribution (CC-BY) License true eng http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html
title Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
spellingShingle Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
Emrys Evans
title_short 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_sort Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers
author_id_str_mv 538e217307dac24c9642ef1b03b41485
author_id_fullname_str_mv 538e217307dac24c9642ef1b03b41485_***_Emrys Evans
author Emrys Evans
author2 Jake L. Greenfield
Emrys Evans
Daniele Di Nuzzo
Marco Di Antonio
Richard H. Friend
Jonathan R. Nitschke
format Journal article
container_title Journal of the American Chemical Society
container_volume 140
container_issue 32
container_start_page 10344
publishDate 2018
institution Swansea University
issn 0002-7863
1520-5126
doi_str_mv 10.1021/jacs.8b06195
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description 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.
published_date 2018-08-15T02:17:11Z
_version_ 1821279447245914112
score 11.047306

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