Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series

Modulation of the packing of the donors in the solid state and of the conducting behaviour is achieved in chiral radical cation salts based on the mono-alkylated donors methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF 1) and ethyl-ethylenedithio-tetrathiafulvalene (Et-EDT-TTF 2), underlining the...

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Autores: Mroweh, Nabil, Auban-Senzier, Pascale, Vanthuyne, Nicolas, Canadell, Enric, Avarvari, Narcis
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/193441
Acceso en línea:http://hdl.handle.net/10261/193441
Access Level:acceso abierto
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spelling Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) seriesMroweh, NabilAuban-Senzier, PascaleVanthuyne, NicolasCanadell, EnricAvarvari, NarcisModulation of the packing of the donors in the solid state and of the conducting behaviour is achieved in chiral radical cation salts based on the mono-alkylated donors methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF 1) and ethyl-ethylenedithio-tetrathiafulvalene (Et-EDT-TTF 2), underlining the paramount role of the number of stereogenic centres and substituent steric hindrance. Both donors have been prepared as racemates and then separated as pure enantiomers by chiral HPLC. Electrocrystallization experiments provided two complete series of crystalline radical cation salts formulated as [(R)-1]2PF6, [(S)-1]2PF6, and [(rac)-1]2PF6 and [(R)-2]2PF6, [(S)-2]2PF6 and [(rac)-2]PF6·(THF), respectively. The mixed valence salts of 1 show metal-like conductivity in the high temperature regime, while the radical cation salts of 2 are semiconductors, with a much higher conductivity for the enantiopure compounds than the racemic one. Tight-binding band structure calculations of the extended Hückel type performed for all the materials explain the observed conducting behaviour and show the differences in the intermolecular interactions triggered by the change of substituent between 1 and 2.This work was supported in France by the National Agency for Research (ANR, Project 15-CE29-0006-01 ChiraMolCo), the CNRS and the University of Angers. Work at Bellaterra (Spain) was supported by the Spanish MICIU through Grant PGC2018-096955-B-C44 and the MINECO through the Severo Ochoa Centers of Excellence Program under Grant SEV-2015-0496 as well as by Generalitat de Catalunya (2017SGR1506).Peer reviewedRoyal Society of Chemistry (UK)Agence Nationale de la Recherche (France)Centre National de la Recherche Scientifique (France)Université d’AngersMinisterio de Ciencia, Innovación y Universidades (España)Ministerio de Economía y Competitividad (España)Generalitat de CatalunyaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201920192019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/193441reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#MICIU/ICTI2017-2020/PGC2018-096955-B-C44info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2015-0496http://dx.doi.org/10.1039/c9tc04243aSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1934412026-05-22T06:33:51Z
dc.title.none.fl_str_mv Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
title Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
spellingShingle Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
Mroweh, Nabil
title_short Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
title_full Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
title_fullStr Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
title_full_unstemmed Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
title_sort Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF)2PF6 (R = Me or Et) series
dc.creator.none.fl_str_mv Mroweh, Nabil
Auban-Senzier, Pascale
Vanthuyne, Nicolas
Canadell, Enric
Avarvari, Narcis
author Mroweh, Nabil
author_facet Mroweh, Nabil
Auban-Senzier, Pascale
Vanthuyne, Nicolas
Canadell, Enric
Avarvari, Narcis
author_role author
author2 Auban-Senzier, Pascale
Vanthuyne, Nicolas
Canadell, Enric
Avarvari, Narcis
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Agence Nationale de la Recherche (France)
Centre National de la Recherche Scientifique (France)
Université d’Angers
Ministerio de Ciencia, Innovación y Universidades (España)
Ministerio de Economía y Competitividad (España)
Generalitat de Catalunya
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Modulation of the packing of the donors in the solid state and of the conducting behaviour is achieved in chiral radical cation salts based on the mono-alkylated donors methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF 1) and ethyl-ethylenedithio-tetrathiafulvalene (Et-EDT-TTF 2), underlining the paramount role of the number of stereogenic centres and substituent steric hindrance. Both donors have been prepared as racemates and then separated as pure enantiomers by chiral HPLC. Electrocrystallization experiments provided two complete series of crystalline radical cation salts formulated as [(R)-1]2PF6, [(S)-1]2PF6, and [(rac)-1]2PF6 and [(R)-2]2PF6, [(S)-2]2PF6 and [(rac)-2]PF6·(THF), respectively. The mixed valence salts of 1 show metal-like conductivity in the high temperature regime, while the radical cation salts of 2 are semiconductors, with a much higher conductivity for the enantiopure compounds than the racemic one. Tight-binding band structure calculations of the extended Hückel type performed for all the materials explain the observed conducting behaviour and show the differences in the intermolecular interactions triggered by the change of substituent between 1 and 2.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/193441
url http://hdl.handle.net/10261/193441
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
MICIU/ICTI2017-2020/PGC2018-096955-B-C44
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2015-0496
http://dx.doi.org/10.1039/c9tc04243a
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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