Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts

Methyl- and dimethyl-ethylenedithio-tetrathiafulvalene ortho-diamide donors Me-EDT-TTF(CONH2)2 (1a) and DM-EDT- TTF(CONH2)2 (1b) have been prepared by the direct reaction of the corresponding diester precursors with aqueous ammonia solutions. The neutral (rac)-1a, (R)-1a, and (S,S)-1b donors have be...

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Autores: Mroweh, Nabil, Pop, Flavia, Mézière, Cécile, Allain, Magali, Auban-Senzier, Pascale, Vanthuyne, Nicolas, Alemany i Cahner, Pere, Canadell, Enric, 1950-, Avarvari, Narcis
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/184513
Acceso en línea:https://hdl.handle.net/2445/184513
Access Level:acceso abierto
Palabra clave:Semiconductors
Molècules
Sal
Molecules
Salt
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spelling Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation saltsMroweh, NabilPop, FlaviaMézière, CécileAllain, MagaliAuban-Senzier, PascaleVanthuyne, NicolasAlemany i Cahner, PereCanadell, Enric, 1950-Avarvari, NarcisSemiconductorsMolèculesSalSemiconductorsMoleculesSaltMethyl- and dimethyl-ethylenedithio-tetrathiafulvalene ortho-diamide donors Me-EDT-TTF(CONH2)2 (1a) and DM-EDT- TTF(CONH2)2 (1b) have been prepared by the direct reaction of the corresponding diester precursors with aqueous ammonia solutions. The neutral (rac)-1a, (R)-1a, and (S,S)-1b donors have been characterized by single crystal X-ray diffraction. In the three compounds, which crystallized in the non-centrosymmetric monoclinic space group P21, the amide groups are disordered, yet they form the classical intra-molecular hydrogen bond for such an ortho-diamide motif. Electro- crystallization experiments afforded the mixed valence radical cation salts[(S,S)-1b]2XO4 and [(R,R)-1b]2XO4 (X = Cl, Re) containing four independent donors in the asymmetric unit, with the positive charge localized essentially on two donors, while the two others are neutral. The topology of the organic layer is of β′-type. Single crystal resistivity measurements show semiconducting behavior for [(S,S)-1b]2ClO4 and [(R,R)-1b]2ReO4, with a room temperature conductivity of 5 × 10−5 S cm−1 and activation energies Ea ≈ 3000 K. Tight-binding band structure calculations of extended Hückel type in combination with density functional theory calculations are in agreement with the semiconducting behavior and suggest a localized Mott type semiconductor rather than a band gap semiconductor.American Chemical Society2020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/184513Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1021/acs.cgd.9b01665Crystal Growth & Design, 2020, vol. 20, num. 4, p. 2516-2526https://doi.org/10.1021/acs.cgd.9b01665(c) American Chemical Society , 2020info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1845132026-05-27T06:46:51Z
dc.title.none.fl_str_mv Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
title Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
spellingShingle Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
Mroweh, Nabil
Semiconductors
Molècules
Sal
Semiconductors
Molecules
Salt
title_short Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
title_full Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
title_fullStr Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
title_full_unstemmed Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
title_sort Combining chirality and hydrogen bonding in methylated ethylenedithio- tetrathiafulvalene primary diamide precursors and radical cation salts
dc.creator.none.fl_str_mv Mroweh, Nabil
Pop, Flavia
Mézière, Cécile
Allain, Magali
Auban-Senzier, Pascale
Vanthuyne, Nicolas
Alemany i Cahner, Pere
Canadell, Enric, 1950-
Avarvari, Narcis
author Mroweh, Nabil
author_facet Mroweh, Nabil
Pop, Flavia
Mézière, Cécile
Allain, Magali
Auban-Senzier, Pascale
Vanthuyne, Nicolas
Alemany i Cahner, Pere
Canadell, Enric, 1950-
Avarvari, Narcis
author_role author
author2 Pop, Flavia
Mézière, Cécile
Allain, Magali
Auban-Senzier, Pascale
Vanthuyne, Nicolas
Alemany i Cahner, Pere
Canadell, Enric, 1950-
Avarvari, Narcis
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Semiconductors
Molècules
Sal
Semiconductors
Molecules
Salt
topic Semiconductors
Molècules
Sal
Semiconductors
Molecules
Salt
description Methyl- and dimethyl-ethylenedithio-tetrathiafulvalene ortho-diamide donors Me-EDT-TTF(CONH2)2 (1a) and DM-EDT- TTF(CONH2)2 (1b) have been prepared by the direct reaction of the corresponding diester precursors with aqueous ammonia solutions. The neutral (rac)-1a, (R)-1a, and (S,S)-1b donors have been characterized by single crystal X-ray diffraction. In the three compounds, which crystallized in the non-centrosymmetric monoclinic space group P21, the amide groups are disordered, yet they form the classical intra-molecular hydrogen bond for such an ortho-diamide motif. Electro- crystallization experiments afforded the mixed valence radical cation salts[(S,S)-1b]2XO4 and [(R,R)-1b]2XO4 (X = Cl, Re) containing four independent donors in the asymmetric unit, with the positive charge localized essentially on two donors, while the two others are neutral. The topology of the organic layer is of β′-type. Single crystal resistivity measurements show semiconducting behavior for [(S,S)-1b]2ClO4 and [(R,R)-1b]2ReO4, with a room temperature conductivity of 5 × 10−5 S cm−1 and activation energies Ea ≈ 3000 K. Tight-binding band structure calculations of extended Hückel type in combination with density functional theory calculations are in agreement with the semiconducting behavior and suggest a localized Mott type semiconductor rather than a band gap semiconductor.
publishDate 2020
dc.date.none.fl_str_mv 2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/184513
url https://hdl.handle.net/2445/184513
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/acs.cgd.9b01665
Crystal Growth & Design, 2020, vol. 20, num. 4, p. 2516-2526
https://doi.org/10.1021/acs.cgd.9b01665
dc.rights.none.fl_str_mv (c) American Chemical Society , 2020
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2020
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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