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Title: Electron Transfer from Photoexcited Naphthalene Diimide Radical Anion to Electrocatalytically Active Re(bpy)(CO) 3 Cl in a Molecular Triad

Abstract

Electron donor–acceptor photosensitizers having long charge separation lifetimes and high-reducing potentials that can be easily appended to thermodynamically difficult to reduce catalysts hold great promise for driving CO 2 reduction. We introduce a new molecular triad utilizing a naphthalene diimide radical anion (NDI •–) donor chromophore appended to a 9,10-diphenylanthracene (DPA) acceptor, which is in turn linked to Re(bpy)(CO)3Cl. The NDI •– chromophore is readily generated by mild chemical or electrochemical reduction, absorbs at wavelengths as long as 800 nm, and has an excited state oxidation potential (–2.1 V vs SCE), which rivals or exceeds those of metalorganic and organometallic chromophores. Photoexcitation of NDI •– to *NDI •– is followed by ultrafast reduction of DPA to DPA •–, which then rapidly reduces the metal complex. The overall quantum yield for reduction of Re(bpy)(CO) 3Cl is approximately 90% using visible light. The general time constant for the forward electron transfer to reduce the metal complex is τ = 14.5 ps, while the time constant for back-electron transfer is τ = 24.5 ns. Under typical electrocatalytic conditions, the molecular triad demonstrates electrochemical reduction of CO 2.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States). Energy Frontier Research Center (EFRC) Argonne-Northwestern Solar Energy Research (ANSER) Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1470239
Grant/Contract Number:  
SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 5; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 14 SOLAR ENERGY

Citation Formats

Martinez, Jose F., La Porte, Nathan T., and Wasielewski, Michael R. Electron Transfer from Photoexcited Naphthalene Diimide Radical Anion to Electrocatalytically Active Re(bpy)(CO)3 Cl in a Molecular Triad. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b11999.
Martinez, Jose F., La Porte, Nathan T., & Wasielewski, Michael R. Electron Transfer from Photoexcited Naphthalene Diimide Radical Anion to Electrocatalytically Active Re(bpy)(CO)3 Cl in a Molecular Triad. United States. doi:10.1021/acs.jpcc.7b11999.
Martinez, Jose F., La Porte, Nathan T., and Wasielewski, Michael R. Fri . "Electron Transfer from Photoexcited Naphthalene Diimide Radical Anion to Electrocatalytically Active Re(bpy)(CO)3 Cl in a Molecular Triad". United States. doi:10.1021/acs.jpcc.7b11999. https://www.osti.gov/servlets/purl/1470239.
@article{osti_1470239,
title = {Electron Transfer from Photoexcited Naphthalene Diimide Radical Anion to Electrocatalytically Active Re(bpy)(CO)3 Cl in a Molecular Triad},
author = {Martinez, Jose F. and La Porte, Nathan T. and Wasielewski, Michael R.},
abstractNote = {Electron donor–acceptor photosensitizers having long charge separation lifetimes and high-reducing potentials that can be easily appended to thermodynamically difficult to reduce catalysts hold great promise for driving CO2 reduction. We introduce a new molecular triad utilizing a naphthalene diimide radical anion (NDI•–) donor chromophore appended to a 9,10-diphenylanthracene (DPA) acceptor, which is in turn linked to Re(bpy)(CO)3Cl. The NDI•– chromophore is readily generated by mild chemical or electrochemical reduction, absorbs at wavelengths as long as 800 nm, and has an excited state oxidation potential (–2.1 V vs SCE), which rivals or exceeds those of metalorganic and organometallic chromophores. Photoexcitation of NDI•– to *NDI•– is followed by ultrafast reduction of DPA to DPA•–, which then rapidly reduces the metal complex. The overall quantum yield for reduction of Re(bpy)(CO)3Cl is approximately 90% using visible light. The general time constant for the forward electron transfer to reduce the metal complex is τ = 14.5 ps, while the time constant for back-electron transfer is τ = 24.5 ns. Under typical electrocatalytic conditions, the molecular triad demonstrates electrochemical reduction of CO2.},
doi = {10.1021/acs.jpcc.7b11999},
journal = {Journal of Physical Chemistry. C},
number = 5,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}

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