skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 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.

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); 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. https://doi.org/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. https://doi.org/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. https://doi.org/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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Remote site photosubstitution in metalloporphyrin–rhenium tricarbonylbipyridine assemblies: photo-reactions of molecules with very short lived excited states
journal, January 2008

  • Gabrielsson, Anders; Lindsay Smith, John R.; Perutz, Robin N.
  • Dalton Transactions, Issue 32
  • DOI: 10.1039/b806267f

A novel ruthenium(II) tris(bipyridine)–zinc porphyrin–rhenium carbonyl triad: synthesis and optical properties
journal, April 2006


Chemical Redox Agents for Organometallic Chemistry
journal, January 1996

  • Connelly, Neil G.; Geiger, William E.
  • Chemical Reviews, Vol. 96, Issue 2
  • DOI: 10.1021/cr940053x

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Supramolecular electrochemistry
journal, March 1991

  • Roffia, Sergio; Casadei, Roberto; Paolucci, Francesco
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 302, Issue 1-2
  • DOI: 10.1016/0022-0728(91)85038-Q

    Works referencing / citing this record:

    Supramolecular Chiral Helical Ribbons of Tetraphenylethylene-Appended Naphthalenediimide Controlled by Solvent and Induced by l - and d -Alanine Spacers
    journal, November 2018

    • Goskulwad, Santosh P.; Kobaisi, Mohammad Al; La, Duong Duc
    • Chemistry - An Asian Journal, Vol. 13, Issue 24
    • DOI: 10.1002/asia.201801421

    Electron transfer reactions in sub-porphyrin–naphthyldiimide dyads
    journal, January 2019

    • Küçüköz, Betül; Adinarayana, B.; Osuka, Atsuhiro
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 30
    • DOI: 10.1039/c9cp03725j

    Covalently linking CuInS 2 quantum dots with a Re catalyst by click reaction for photocatalytic CO 2 reduction
    journal, January 2018

    • Huang, Jing; Gatty, Mélina Gilbert; Xu, Bo
    • Dalton Transactions, Vol. 47, Issue 31
    • DOI: 10.1039/c8dt01631c