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dc.contributor.author
Odella, Emmanuel
dc.contributor.author
Secor, Maxim
dc.contributor.author
Reyes Cruz, Edgar A.
dc.contributor.author
Guerra, Walter D.
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Urrutia, María Noel
dc.contributor.author
Liddell, Paul A.
dc.contributor.author
Moore, Thomas A.
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Moore, Gary F.
dc.contributor.author
Hammes Schiffer, Sharon
dc.contributor.author
Moore, Ana L.
dc.date.available
2023-07-10T12:10:13Z
dc.date.issued
2022-08
dc.identifier.citation
Odella, Emmanuel; Secor, Maxim; Reyes Cruz, Edgar A.; Guerra, Walter D.; Urrutia, María Noel; et al.; Managing the Redox Potential of PCET in Grotthuss-Type Proton Wires; American Chemical Society; Journal of the American Chemical Society; 144; 34; 8-2022; 15672-15679
dc.identifier.issn
0002-7863
dc.identifier.uri
http://hdl.handle.net/11336/202848
dc.description.abstract
Expanding proton-coupled electron transfer to multiproton translocations (MPCET) provides a bioinspired mechanism to transport protons away from the redox site. This expansion has been accomplished by separating the initial phenolic proton donor from the pyridine-based terminal proton acceptor by a Grotthuss-type proton wire made up of concatenated benzimidazoles that form a hydrogen-bonded network. However, it was found that the midpoint potential of the phenol oxidation that launched the Grotthuss-type proton translocations is a function of the number of benzimidazoles in the hydrogen-bonded network; it becomes less positive (i.e., a weaker oxidant) as the number of bridging benzimidazoles increases. Herein, we report a strategy to maintain the high redox potential necessary for oxidative processes relevant to artificial photosynthesis, e.g., water oxidation and long-range MPCET processes for managing protons. The integrated structural and functional roles of the benzimidazole-based bridge provide sites for substitution of the benzimidazoles with electron-withdrawing groups (e.g., trifluoromethyl groups). Such substitution increases the midpoint potential of the phenoxyl radical/phenol couple so that proton translocations over ∼11 Å become thermodynamically comparable to that of an unsubstituted system where one proton is transferred over ∼2.5 Å. The extended, substituted system maintains the hydrogen-bonded network; infrared spectroelectrochemistry confirms reversible proton translocations from the phenol to the pyridyl terminal proton acceptor upon oxidation and reduction. Theory supports the change in driving force with added electron-withdrawing groups and provides insight into the role of electron density and electrostatic potential in MPCET processes associated with these Grotthuss-type proton translocations.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
REDOX POTENTIAL
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BENZIMIDAZOLE PHENOL (BIP)
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ELECTRON WITHDRAWING GROUP
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Química Orgánica
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Managing the Redox Potential of PCET in Grotthuss-Type Proton Wires
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2023-07-05T12:07:16Z
dc.journal.volume
144
dc.journal.number
34
dc.journal.pagination
15672-15679
dc.journal.pais
Estados Unidos
dc.description.fil
Fil: Odella, Emmanuel. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil
Fil: Secor, Maxim. University of Yale; Estados Unidos
dc.description.fil
Fil: Reyes Cruz, Edgar A.. Arizona State University; Estados Unidos
dc.description.fil
Fil: Guerra, Walter D.. Arizona State University; Estados Unidos
dc.description.fil
Fil: Urrutia, María Noel. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
dc.description.fil
Fil: Liddell, Paul A.. Arizona State University; Estados Unidos
dc.description.fil
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
dc.description.fil
Fil: Moore, Gary F.. Arizona State University; Estados Unidos
dc.description.fil
Fil: Hammes Schiffer, Sharon. University of Yale; Estados Unidos
dc.description.fil
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
dc.journal.title
Journal of the American Chemical Society
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jacs.2c05820
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jacs.2c05820
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