Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

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

doi:10.1021/jacs.8b06195

Journal article 826 views 83 downloads

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

Jake L. Greenfield, Emrys Evans

, 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

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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
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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 CHEM 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 Chemistry COLLEGE CODE CHEM 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	2018-08-15T04:13:25Z
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score	11.0267

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

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