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Title: Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires

Abstract

Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI2P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pKa units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI2P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group.more » The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular “dry proton wires” with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. School of Molecular Sciences, Arizona State University, Tempe, USA
  2. Department of Chemistry, Yale University, New Haven, USA
  3. Departamento de Química, Facultad de Ciencias Exactas, Físico-Químicas y Naturales, Universidad Nacional de Río Cuarto, 5800 Río Cuarto, Argentina
Publication Date:
Research Org.:
Arizona State Univ., Tempe, AZ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1606458
Alternate Identifier(s):
OSTI ID: 1800066
Grant/Contract Number:  
FG02-03ER15393
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 15; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Odella, Emmanuel, Mora, S. Jimena, Wadsworth, Brian L., Goings, Joshua J., Gervaldo, Miguel A., Sereno, Leonides E., Groy, Thomas L., Gust, Devens, Moore, Thomas A., Moore, Gary F., Hammes-Schiffer, Sharon, and Moore, Ana L. Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires. United Kingdom: N. p., 2020. Web. doi:10.1039/C9SC06010C.
Odella, Emmanuel, Mora, S. Jimena, Wadsworth, Brian L., Goings, Joshua J., Gervaldo, Miguel A., Sereno, Leonides E., Groy, Thomas L., Gust, Devens, Moore, Thomas A., Moore, Gary F., Hammes-Schiffer, Sharon, & Moore, Ana L. Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires. United Kingdom. https://doi.org/10.1039/C9SC06010C
Odella, Emmanuel, Mora, S. Jimena, Wadsworth, Brian L., Goings, Joshua J., Gervaldo, Miguel A., Sereno, Leonides E., Groy, Thomas L., Gust, Devens, Moore, Thomas A., Moore, Gary F., Hammes-Schiffer, Sharon, and Moore, Ana L. Wed . "Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires". United Kingdom. https://doi.org/10.1039/C9SC06010C.
@article{osti_1606458,
title = {Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires},
author = {Odella, Emmanuel and Mora, S. Jimena and Wadsworth, Brian L. and Goings, Joshua J. and Gervaldo, Miguel A. and Sereno, Leonides E. and Groy, Thomas L. and Gust, Devens and Moore, Thomas A. and Moore, Gary F. and Hammes-Schiffer, Sharon and Moore, Ana L.},
abstractNote = {Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI2P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pKa units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI2P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group. The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular “dry proton wires” with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.},
doi = {10.1039/C9SC06010C},
journal = {Chemical Science},
number = 15,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {4}
}

Journal Article:
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https://doi.org/10.1039/C9SC06010C

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