Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires
Charge transfer/transport in molecular wires over varying distances is a subject of great interest. The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping t...
| Autores: | , , , , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/124977 |
| Acceso en línea: | https://hdl.handle.net/2445/124977 |
| Access Level: | acceso abierto |
| Palabra clave: | Transferència de càrrega Transport d'electrons Cinètica química Espectroscòpia Raman Química quàntica Charge transfer Electron transport Chemical kinetics Raman spectroscopy Quantum chemistry |
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oai:recercat.cat:2445/124977 |
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Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wiresFranco, CarlosMayorga Burrezo, PaulaLloveras, VegaCaballero, RubenAlcón Rovira, IsaacBromley, Stefan ThomasMas Torrent, MartaLanga, FernandoLópez Navarrete, Juan T.Rovira i Angulo, ConcepcióCasado, JuanVeciana, JaumeTransferència de càrregaTransport d'electronsCinètica químicaEspectroscòpia RamanQuímica quànticaCharge transferElectron transportChemical kineticsRaman spectroscopyQuantum chemistryCharge transfer/transport in molecular wires over varying distances is a subject of great interest. The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping transport over larger distances. The underlying molecular sequential steps that likely take place during hopping and the operative mechanism occurring at intermediate distances have received much less attention given the difficulty in assessing detailed molecular-level information. We describe here the operating mechanisms for unimolecular electron transfer/transport in the ground state of radical-anion mixed-valence derivatives occurring between their terminal perchlorotriphenylmethyl/ide groups through thiophene-vinylene oligomers that act as conjugated wires of increasing length up to 53 angstrom, The unique finding here is that the net transport of the electron in the larger molecular wires is initiated by an electron hole dissociation intermediated by hole delocalization (conformationally assisted and thermally dependent) forming transient mobile polaronic states in the bridge that terminate by an electron hole recombination at the other wire extreme. On the contrary, for the shorter radical-anions our results suggest that a flickering resonance mechanism which is intermediate between hopping and superexchange is the operative one. We support these mechanistic interpretations by applying the pertinent biased kinetic models of the charge/spin exchange rates determined by electron paramagnetic resonance and by molecular structural level information obtained from UV-vis and Raman spectroscopies and by quantum chemical modeling.American Chemical Society2018201820172018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion7 p.application/pdfhttps://hdl.handle.net/2445/124977Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1021/jacs.6b08649Journal of the American Chemical Society, 2017, vol. 139, num. 2, p. 686-692https://doi.org/10.1021/jacs.6b08649(c) American Chemical Society , 2017info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1249772026-05-29T05:05:01Z |
| dc.title.none.fl_str_mv |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| title |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| spellingShingle |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires Franco, Carlos Transferència de càrrega Transport d'electrons Cinètica química Espectroscòpia Raman Química quàntica Charge transfer Electron transport Chemical kinetics Raman spectroscopy Quantum chemistry |
| title_short |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| title_full |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| title_fullStr |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| title_full_unstemmed |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| title_sort |
Operative mechanism of hole-assisted negative charge motion in ground states of radical-anion molecular wires |
| dc.creator.none.fl_str_mv |
Franco, Carlos Mayorga Burrezo, Paula Lloveras, Vega Caballero, Ruben Alcón Rovira, Isaac Bromley, Stefan Thomas Mas Torrent, Marta Langa, Fernando López Navarrete, Juan T. Rovira i Angulo, Concepció Casado, Juan Veciana, Jaume |
| author |
Franco, Carlos |
| author_facet |
Franco, Carlos Mayorga Burrezo, Paula Lloveras, Vega Caballero, Ruben Alcón Rovira, Isaac Bromley, Stefan Thomas Mas Torrent, Marta Langa, Fernando López Navarrete, Juan T. Rovira i Angulo, Concepció Casado, Juan Veciana, Jaume |
| author_role |
author |
| author2 |
Mayorga Burrezo, Paula Lloveras, Vega Caballero, Ruben Alcón Rovira, Isaac Bromley, Stefan Thomas Mas Torrent, Marta Langa, Fernando López Navarrete, Juan T. Rovira i Angulo, Concepció Casado, Juan Veciana, Jaume |
| author2_role |
author author author author author author author author author author author |
| dc.subject.none.fl_str_mv |
Transferència de càrrega Transport d'electrons Cinètica química Espectroscòpia Raman Química quàntica Charge transfer Electron transport Chemical kinetics Raman spectroscopy Quantum chemistry |
| topic |
Transferència de càrrega Transport d'electrons Cinètica química Espectroscòpia Raman Química quàntica Charge transfer Electron transport Chemical kinetics Raman spectroscopy Quantum chemistry |
| description |
Charge transfer/transport in molecular wires over varying distances is a subject of great interest. The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping transport over larger distances. The underlying molecular sequential steps that likely take place during hopping and the operative mechanism occurring at intermediate distances have received much less attention given the difficulty in assessing detailed molecular-level information. We describe here the operating mechanisms for unimolecular electron transfer/transport in the ground state of radical-anion mixed-valence derivatives occurring between their terminal perchlorotriphenylmethyl/ide groups through thiophene-vinylene oligomers that act as conjugated wires of increasing length up to 53 angstrom, The unique finding here is that the net transport of the electron in the larger molecular wires is initiated by an electron hole dissociation intermediated by hole delocalization (conformationally assisted and thermally dependent) forming transient mobile polaronic states in the bridge that terminate by an electron hole recombination at the other wire extreme. On the contrary, for the shorter radical-anions our results suggest that a flickering resonance mechanism which is intermediate between hopping and superexchange is the operative one. We support these mechanistic interpretations by applying the pertinent biased kinetic models of the charge/spin exchange rates determined by electron paramagnetic resonance and by molecular structural level information obtained from UV-vis and Raman spectroscopies and by quantum chemical modeling. |
| publishDate |
2017 |
| dc.date.none.fl_str_mv |
2017 2018 2018 2018 |
| 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/2445/124977 |
| url |
https://hdl.handle.net/2445/124977 |
| 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/jacs.6b08649 Journal of the American Chemical Society, 2017, vol. 139, num. 2, p. 686-692 https://doi.org/10.1021/jacs.6b08649 |
| dc.rights.none.fl_str_mv |
(c) American Chemical Society , 2017 info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
(c) American Chemical Society , 2017 |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
7 p. 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:Recercat. Dipósit de la Recerca de Catalunya instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| instname_str |
Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| reponame_str |
Recercat. Dipósit de la Recerca de Catalunya |
| collection |
Recercat. Dipósit de la Recerca de Catalunya |
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1869403469128925184 |
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15,811543 |