Role of intact hydrogen-bond networks in multiproton-coupled electron transfer
- Autores
- Guerra, Walter Damián; Odella, Emmanuel; Secor, Maxim; Goings, Joshua J.; Urrutia, María N.; Wadsworth, Brian L.; Gervaldo, Miguel Andres; Sereno, Leonides Edmundo; Moore, Thomas A.; Moore, Gary F.; Hammes-Schiffer, Sharon; Moore, Ana L.
- Año de publicación
- 2020
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (μ1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.
Fil: Guerra, Walter Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Arizona State University; Estados Unidos
Fil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Secor, Maxim. University of Yale; Estados Unidos
Fil: Goings, Joshua J.. University of Yale; Estados Unidos
Fil: Urrutia, María N.. Arizona State University; Estados Unidos
Fil: Wadsworth, Brian L.. Arizona State University; Estados Unidos
Fil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Moore, Gary F.. Arizona State University; Estados Unidos
Fil: Hammes-Schiffer, Sharon. University of Yale; Estados Unidos
Fil: Moore, Ana L.. University of Yale; Estados Unidos - Materia
-
Proton-coupled electron transfer
Benzimidazole−phenol
Cyclic voltammetry
Bioinspired assemblies - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/136290
Ver los metadatos del registro completo
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Role of intact hydrogen-bond networks in multiproton-coupled electron transferGuerra, Walter DamiánOdella, EmmanuelSecor, MaximGoings, Joshua J.Urrutia, María N.Wadsworth, Brian L.Gervaldo, Miguel AndresSereno, Leonides EdmundoMoore, Thomas A.Moore, Gary F.Hammes-Schiffer, SharonMoore, Ana L.Proton-coupled electron transferBenzimidazole−phenolCyclic voltammetryBioinspired assemblieshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (μ1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.Fil: Guerra, Walter Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Arizona State University; Estados UnidosFil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Secor, Maxim. University of Yale; Estados UnidosFil: Goings, Joshua J.. University of Yale; Estados UnidosFil: Urrutia, María N.. Arizona State University; Estados UnidosFil: Wadsworth, Brian L.. Arizona State University; Estados UnidosFil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Moore, Thomas A.. Arizona State University; Estados UnidosFil: Moore, Gary F.. Arizona State University; Estados UnidosFil: Hammes-Schiffer, Sharon. University of Yale; Estados UnidosFil: Moore, Ana L.. University of Yale; Estados UnidosAmerican Chemical Society2020-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/136290Guerra, Walter Damián; Odella, Emmanuel; Secor, Maxim; Goings, Joshua J.; Urrutia, María N.; et al.; Role of intact hydrogen-bond networks in multiproton-coupled electron transfer; American Chemical Society; Journal of the American Chemical Society; 142; 52; 12-2020; 21842-218510002-78631520-5126CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jacs.0c10474info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.0c10474info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:28:06Zoai:ri.conicet.gov.ar:11336/136290instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:28:06.883CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
title |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
spellingShingle |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer Guerra, Walter Damián Proton-coupled electron transfer Benzimidazole−phenol Cyclic voltammetry Bioinspired assemblies |
title_short |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
title_full |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
title_fullStr |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
title_full_unstemmed |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
title_sort |
Role of intact hydrogen-bond networks in multiproton-coupled electron transfer |
dc.creator.none.fl_str_mv |
Guerra, Walter Damián Odella, Emmanuel Secor, Maxim Goings, Joshua J. Urrutia, María N. Wadsworth, Brian L. Gervaldo, Miguel Andres Sereno, Leonides Edmundo Moore, Thomas A. Moore, Gary F. Hammes-Schiffer, Sharon Moore, Ana L. |
author |
Guerra, Walter Damián |
author_facet |
Guerra, Walter Damián Odella, Emmanuel Secor, Maxim Goings, Joshua J. Urrutia, María N. Wadsworth, Brian L. Gervaldo, Miguel Andres Sereno, Leonides Edmundo Moore, Thomas A. Moore, Gary F. Hammes-Schiffer, Sharon Moore, Ana L. |
author_role |
author |
author2 |
Odella, Emmanuel Secor, Maxim Goings, Joshua J. Urrutia, María N. Wadsworth, Brian L. Gervaldo, Miguel Andres Sereno, Leonides Edmundo Moore, Thomas A. Moore, Gary F. Hammes-Schiffer, Sharon Moore, Ana L. |
author2_role |
author author author author author author author author author author author |
dc.subject.none.fl_str_mv |
Proton-coupled electron transfer Benzimidazole−phenol Cyclic voltammetry Bioinspired assemblies |
topic |
Proton-coupled electron transfer Benzimidazole−phenol Cyclic voltammetry Bioinspired assemblies |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (μ1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism. Fil: Guerra, Walter Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Arizona State University; Estados Unidos Fil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Secor, Maxim. University of Yale; Estados Unidos Fil: Goings, Joshua J.. University of Yale; Estados Unidos Fil: Urrutia, María N.. Arizona State University; Estados Unidos Fil: Wadsworth, Brian L.. Arizona State University; Estados Unidos Fil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Moore, Thomas A.. Arizona State University; Estados Unidos Fil: Moore, Gary F.. Arizona State University; Estados Unidos Fil: Hammes-Schiffer, Sharon. University of Yale; Estados Unidos Fil: Moore, Ana L.. University of Yale; Estados Unidos |
description |
The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (μ1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-12 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/136290 Guerra, Walter Damián; Odella, Emmanuel; Secor, Maxim; Goings, Joshua J.; Urrutia, María N.; et al.; Role of intact hydrogen-bond networks in multiproton-coupled electron transfer; American Chemical Society; Journal of the American Chemical Society; 142; 52; 12-2020; 21842-21851 0002-7863 1520-5126 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/136290 |
identifier_str_mv |
Guerra, Walter Damián; Odella, Emmanuel; Secor, Maxim; Goings, Joshua J.; Urrutia, María N.; et al.; Role of intact hydrogen-bond networks in multiproton-coupled electron transfer; American Chemical Society; Journal of the American Chemical Society; 142; 52; 12-2020; 21842-21851 0002-7863 1520-5126 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jacs.0c10474 info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.0c10474 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf 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 |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844614284420579328 |
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13.070432 |