No Cover Image

Journal article 543 views 142 downloads

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

Jake L. Greenfield, Daniele Di Nuzzo, Emrys Evans Orcid Logo, Satyaprasad P. Senanayak, Sam Schott, Jason T. Deacon, Adele Peugeot, William K. Myers, Henning Sirringhaus, Richard H. Friend, Jonathan R. Nitschke

Advanced Materials, Volume: 33, Issue: 24, Start page: 2100403

Swansea University Author: Emrys Evans Orcid Logo

  • 57562.pdf

    PDF | Version of Record

    © 2021 The Authors. This is an open access article under the terms of the Creative Commons Attribution License

    Download (2.61MB)

Check full text

DOI (Published version): 10.1002/adma.202100403

Abstract

Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the m...

Full description

Published in: Advanced Materials
ISSN: 0935-9648 1521-4095
Published: Wiley 2021
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa57562
Tags: Add Tag
No Tags, Be the first to tag this record!
first_indexed 2021-08-10T08:16:07Z
last_indexed 2021-09-10T03:20:19Z
id cronfa57562
recordtype SURis
fullrecord <?xml version="1.0"?><rfc1807><datestamp>2021-09-09T12:23:39.8983657</datestamp><bib-version>v2</bib-version><id>57562</id><entry>2021-08-10</entry><title>Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers</title><swanseaauthors><author><sid>538e217307dac24c9642ef1b03b41485</sid><ORCID>0000-0002-9092-3938</ORCID><firstname>Emrys</firstname><surname>Evans</surname><name>Emrys Evans</name><active>true</active><ethesisStudent>false</ethesisStudent></author></swanseaauthors><date>2021-08-10</date><deptcode>CHEM</deptcode><abstract>Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that &#x2248;25% of the copper atoms oxidize from CuI to CuII, without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII. This mixed-valence structure exhibits a 104-fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.</abstract><type>Journal Article</type><journal>Advanced Materials</journal><volume>33</volume><journalNumber>24</journalNumber><paginationStart>2100403</paginationStart><paginationEnd/><publisher>Wiley</publisher><placeOfPublication/><isbnPrint/><isbnElectronic/><issnPrint>0935-9648</issnPrint><issnElectronic>1521-4095</issnElectronic><keywords>chirality; metallopolymers; mixed-valency; resistive switching; self-assembly</keywords><publishedDay>17</publishedDay><publishedMonth>6</publishedMonth><publishedYear>2021</publishedYear><publishedDate>2021-06-17</publishedDate><doi>10.1002/adma.202100403</doi><url/><notes/><college>COLLEGE NANME</college><department>Chemistry</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>CHEM</DepartmentCode><institution>Swansea University</institution><apcterm/><funders>UK Engineering and Physical Sciences Research Council. Grant Numbers: EPSRC EP/P027067/1, EP/M01083x/1, EP/M005143/1. European Research Council. Grant Number: ERC695009. ERC Synergy. Grant Number: 610115</funders><lastEdited>2021-09-09T12:23:39.8983657</lastEdited><Created>2021-08-10T09:15:34.9253075</Created><path><level id="1">Faculty of Science and Engineering</level><level id="2">School of Engineering and Applied Sciences - Chemistry</level></path><authors><author><firstname>Jake L.</firstname><surname>Greenfield</surname><order>1</order></author><author><firstname>Daniele Di</firstname><surname>Nuzzo</surname><order>2</order></author><author><firstname>Emrys</firstname><surname>Evans</surname><orcid>0000-0002-9092-3938</orcid><order>3</order></author><author><firstname>Satyaprasad P.</firstname><surname>Senanayak</surname><order>4</order></author><author><firstname>Sam</firstname><surname>Schott</surname><order>5</order></author><author><firstname>Jason T.</firstname><surname>Deacon</surname><order>6</order></author><author><firstname>Adele</firstname><surname>Peugeot</surname><order>7</order></author><author><firstname>William K.</firstname><surname>Myers</surname><order>8</order></author><author><firstname>Henning</firstname><surname>Sirringhaus</surname><order>9</order></author><author><firstname>Richard H.</firstname><surname>Friend</surname><order>10</order></author><author><firstname>Jonathan R.</firstname><surname>Nitschke</surname><order>11</order></author></authors><documents><document><filename>57562__20804__1ab13b540e6e406086c08d617c6735b7.pdf</filename><originalFilename>57562.pdf</originalFilename><uploaded>2021-09-09T12:22:32.5746038</uploaded><type>Output</type><contentLength>2741334</contentLength><contentType>application/pdf</contentType><version>Version of Record</version><cronfaStatus>true</cronfaStatus><documentNotes>&#xA9; 2021 The Authors. This is an open access article under the terms of the Creative Commons Attribution License</documentNotes><copyrightCorrect>true</copyrightCorrect><language>eng</language><licence>http://creativecommons.org/licenses/by/4.0/</licence></document></documents><OutputDurs/></rfc1807>
spelling 2021-09-09T12:23:39.8983657 v2 57562 2021-08-10 Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers 538e217307dac24c9642ef1b03b41485 0000-0002-9092-3938 Emrys Evans Emrys Evans true false 2021-08-10 CHEM Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII, without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII. This mixed-valence structure exhibits a 104-fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale. Journal Article Advanced Materials 33 24 2100403 Wiley 0935-9648 1521-4095 chirality; metallopolymers; mixed-valency; resistive switching; self-assembly 17 6 2021 2021-06-17 10.1002/adma.202100403 COLLEGE NANME Chemistry COLLEGE CODE CHEM Swansea University UK Engineering and Physical Sciences Research Council. Grant Numbers: EPSRC EP/P027067/1, EP/M01083x/1, EP/M005143/1. European Research Council. Grant Number: ERC695009. ERC Synergy. Grant Number: 610115 2021-09-09T12:23:39.8983657 2021-08-10T09:15:34.9253075 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Jake L. Greenfield 1 Daniele Di Nuzzo 2 Emrys Evans 0000-0002-9092-3938 3 Satyaprasad P. Senanayak 4 Sam Schott 5 Jason T. Deacon 6 Adele Peugeot 7 William K. Myers 8 Henning Sirringhaus 9 Richard H. Friend 10 Jonathan R. Nitschke 11 57562__20804__1ab13b540e6e406086c08d617c6735b7.pdf 57562.pdf 2021-09-09T12:22:32.5746038 Output 2741334 application/pdf Version of Record true © 2021 The Authors. This is an open access article under the terms of the Creative Commons Attribution License true eng http://creativecommons.org/licenses/by/4.0/
title Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
spellingShingle Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
Emrys Evans
title_short Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
title_full Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
title_fullStr Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
title_full_unstemmed Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
title_sort Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers
author_id_str_mv 538e217307dac24c9642ef1b03b41485
author_id_fullname_str_mv 538e217307dac24c9642ef1b03b41485_***_Emrys Evans
author Emrys Evans
author2 Jake L. Greenfield
Daniele Di Nuzzo
Emrys Evans
Satyaprasad P. Senanayak
Sam Schott
Jason T. Deacon
Adele Peugeot
William K. Myers
Henning Sirringhaus
Richard H. Friend
Jonathan R. Nitschke
format Journal article
container_title Advanced Materials
container_volume 33
container_issue 24
container_start_page 2100403
publishDate 2021
institution Swansea University
issn 0935-9648
1521-4095
doi_str_mv 10.1002/adma.202100403
publisher Wiley
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 Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII, without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII. This mixed-valence structure exhibits a 104-fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.
published_date 2021-06-17T04:13:24Z
_version_ 1763753909952708608
score 10.999524

Similar Items