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Title: Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

Abstract

To explore the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C 60) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CyP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CyP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of 1P–C 60–CyP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CyP. The P •+–C 60 •––CyP charge-separated state transfers an electron to CyP to produce a final P •+–C 60–CyP •– state. The same state is formed from P–C 601CyP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediatemore » P •+–C 60 •––CyP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. Moreover, this is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Arizona State Univ., Tempe, AZ (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Solar Fuel Production (BISfuel)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1369662
Grant/Contract Number:  
SC0001016; FG02‐03ER15393
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 27; Related Information: BISfuel partners with Arizona State University.; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Antoniuk-Pablant, Antaeres, Kodis, Gerdenis, Moore, Ana L., Moore, Thomas A., and Gust, Devens. Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.6b03470.
Antoniuk-Pablant, Antaeres, Kodis, Gerdenis, Moore, Ana L., Moore, Thomas A., & Gust, Devens. Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator. United States. https://doi.org/10.1021/acs.jpcb.6b03470
Antoniuk-Pablant, Antaeres, Kodis, Gerdenis, Moore, Ana L., Moore, Thomas A., and Gust, Devens. Wed . "Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator". United States. https://doi.org/10.1021/acs.jpcb.6b03470. https://www.osti.gov/servlets/purl/1369662.
@article{osti_1369662,
title = {Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator},
author = {Antoniuk-Pablant, Antaeres and Kodis, Gerdenis and Moore, Ana L. and Moore, Thomas A. and Gust, Devens},
abstractNote = {To explore the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C60) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CyP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CyP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of 1P–C60–CyP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CyP. The P•+–C60•––CyP charge-separated state transfers an electron to CyP to produce a final P•+–C60–CyP•– state. The same state is formed from P–C60–1CyP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediate P•+–C60•––CyP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. Moreover, this is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.},
doi = {10.1021/acs.jpcb.6b03470},
url = {https://www.osti.gov/biblio/1369662}, journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 27,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}

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