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Title: Direct observation of light-driven, concerted electron–proton transfer

Abstract

Here, the phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4'-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron–proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ~1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [3]
+ Show Author Affiliations
  1. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290,
  2. Institute of Environmental Science, Shanxi University, Taiyuan, Shanxi, China 030006,
  3. Department of Chemistry, Memorial University of Newfoundland, St. John’s, NL, A1B 3X7, Canada
Publication Date:
Research Org.:
Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1326239
Alternate Identifier(s):
OSTI ID: 1464947
Grant/Contract Number:  
SC0001011
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 40; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; light driven; electron; proton; transfer; photoEPT

Citation Formats

Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., and Thompson, David W. Direct observation of light-driven, concerted electron–proton transfer. United States: N. p., 2016. Web. doi:10.1073/pnas.1611496113.
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Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., & Thompson, David W. Direct observation of light-driven, concerted electron–proton transfer. United States. https://doi.org/10.1073/pnas.1611496113
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Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., and Thompson, David W. Thu . "Direct observation of light-driven, concerted electron–proton transfer". United States. https://doi.org/10.1073/pnas.1611496113.
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@article{osti_1326239,
title = {Direct observation of light-driven, concerted electron–proton transfer},
author = {Gagliardi, Christopher J. and Wang, Li and Dongare, Prateek and Brennaman, M. Kyle and Papanikolas, John M. and Meyer, Thomas J. and Thompson, David W.},
abstractNote = {Here, the phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4'-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron–proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ~1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.},
doi = {10.1073/pnas.1611496113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 40,
volume = 113,
place = {United States},
year = {Thu Sep 22 00:00:00 EDT 2016},
month = {Thu Sep 22 00:00:00 EDT 2016}
}
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https://doi.org/10.1073/pnas.1611496113
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Works referenced in this record:

Reversible, Long-Range Radical Transfer in E. coli Class Ia Ribonucleotide Reductase
journal, June 2013

  • Minnihan, Ellen C.; Nocera, Daniel G.; Stubbe, JoAnne
  • Accounts of Chemical Research, Vol. 46, Issue 11
  • DOI: 10.1021/ar4000407

Proton-coupled electron transfer: classification scheme and guide to theoretical methods
journal, January 2012

  • Hammes-Schiffer, Sharon
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee03361e

Generation, Characterization, and Deprotonation of Phenol Radical Cations 1
journal, November 1999

  • Gadosy, T. A.; Shukla, D.; Johnston, L. J.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 44
  • DOI: 10.1021/jp992216x

Real-time Simulations of Photoinduced Coherent Charge Transfer and Proton-Coupled Electron Transfer
journal, September 2014

Direct Evidence of a Tryptophan Analogue Radical Formed in a Concerted Electron−Proton Transfer Reaction in Water
journal, February 2016

  • Dongare, Prateek; Maji, Somnath; Hammarström, Leif
  • Journal of the American Chemical Society, Vol. 138, Issue 7
  • DOI: 10.1021/jacs.5b08294

Kinetics of cyclobutane thymine dimer splitting by DNA photolyase directly monitored in the UV
journal, May 2011

  • Thiagarajan, V.; Byrdin, M.; Eker, A. P. M.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 23
  • DOI: 10.1073/pnas.1101026108

Artificial Photosynthesis: Molecular Systems for Catalytic Water Oxidation
journal, October 2014

  • Kärkäs, Markus D.; Verho, Oscar; Johnston, Eric V.
  • Chemical Reviews, Vol. 114, Issue 24
  • DOI: 10.1021/cr400572f

Proton-coupled electron transfer drives the proton pump of cytochrome c oxidase
journal, April 2006

  • Belevich, Ilya; Verkhovsky, Michael I.; Wikström, Mårten
  • Nature, Vol. 440, Issue 7085
  • DOI: 10.1038/nature04619

Direct observation of vibrational coherence in bacterial reaction centers using femtosecond absorption spectroscopy.
journal, October 1991

  • Vos, M. H.; Lambry, J. C.; Robles, S. J.
  • Proceedings of the National Academy of Sciences, Vol. 88, Issue 20
  • DOI: 10.1073/pnas.88.20.8885

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes
journal, May 2011

  • Westlake, B. C.; Brennaman, M. K.; Concepcion, J. J.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 21
  • DOI: 10.1073/pnas.1104811108

Proton-Coupled Electron Transfer
journal, April 2012

  • Weinberg, David R.; Gagliardi, Christopher J.; Hull, Jonathan F.
  • Chemical Reviews, Vol. 112, Issue 7
  • DOI: 10.1021/cr200177j

Redox-Switchable Direction of Photoinduced Electron Transfer in an Ru(bpy)32+-Viologen Dyad
journal, January 2002

Proton-Coupled Electron Transfer
journal, November 2007

  • Huynh, My Hang V.; Meyer, Thomas J.
  • Chemical Reviews, Vol. 107, Issue 11
  • DOI: 10.1021/cr0500030

Proton-Coupled Electron Transfer: Moving Together and Charging Forward
journal, July 2015

  • Hammes-Schiffer, Sharon
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04087

Direct approach to measuring the Franck-Condon barrier to electron transfer between metal ions
journal, July 1969

  • Creutz, Carol; Taube, Henry
  • Journal of the American Chemical Society, Vol. 91, Issue 14
  • DOI: 10.1021/ja01042a072

Mitochondrial formation of reactive oxygen species
journal, October 2003

Investigation of Interligand Electron Transfer in Polypyridyl Complexes of Os(II) Using Femtosecond Polarization Anisotropy Methods:  Examination of Os(bpy) 3 2+ and Os(bpy) 2 (mab) 2+
journal, February 2002

  • Shaw, George B.; Brown, Carter L.; Papanikolas, John M.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 8
  • DOI: 10.1021/jp012924u

Coherence in Energy Transfer and Photosynthesis
journal, April 2015

Excited-State Quenching by Proton-Coupled Electron Transfer
journal, June 2007

  • Concepcion, Javier J.; Brennaman, M. Kyle; Deyton, Jeremy R.
  • Journal of the American Chemical Society, Vol. 129, Issue 22
  • DOI: 10.1021/ja069049g

De Novo Proteins as Models of Radical Enzymes †
journal, July 1999

  • Tommos, Cecilia; Skalicky, Jack J.; Pilloud, Denis L.
  • Biochemistry, Vol. 38, Issue 29
  • DOI: 10.1021/bi990609g

Determining complete electron flow in the cofactor photoreduction of oxidized photolyase
journal, July 2013

  • Liu, Z.; Tan, C.; Guo, X.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 32
  • DOI: 10.1073/pnas.1311073110

When electrons and protons get excited
journal, May 2011

  • Hammes-Schiffer, S.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 21
  • DOI: 10.1073/pnas.1105806108

The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II
journal, July 2007

  • Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden
  • Angewandte Chemie International Edition, Vol. 46, Issue 28
  • DOI: 10.1002/anie.200600917

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer in a Solvated Phenol–Amine Complex
journal, August 2014

  • Goyal, Puja; Schwerdtfeger, Christine A.; Soudackov, Alexander V.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 6
  • DOI: 10.1021/jp5126969

The mechanism for proton–coupled electron transfer from tyrosine in a model complex and comparisons with Y Z oxidation in photosystem II
journal, October 2002

  • Sjödin, Martin; Styring, Stenbjörn; Åkermark, Björn
  • Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences, Vol. 357, Issue 1426
  • DOI: 10.1098/rstb.2002.1142

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

  • Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
  • Chemical Reviews, Vol. 110, Issue 12
  • DOI: 10.1021/cr100085k

Triplet−Triplet Annihilation of Excited States of Polypyridyl Ru(II) Complexes Bound to Polystyrene
journal, June 2002

  • Shaw, George B.; Papanikolas, John M.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 24
  • DOI: 10.1021/jp0145006

Proton and hydrogen currents in photosynthetic water oxidation
journal, May 2000

Electron transfer quenching of excited states of metal complexes
journal, January 1976

  • Young, Roger C.; Meyer, Thomas J.; Whitten, David G.
  • Journal of the American Chemical Society, Vol. 98, Issue 1
  • DOI: 10.1021/ja00417a073

Outer-sphere charge transfer in mixed-metal ion pairs
journal, April 1982

  • Curtis, Jeff C.; Meyer, Thomas J.
  • Inorganic Chemistry, Vol. 21, Issue 4
  • DOI: 10.1021/ic00134a059

Ultrafast Photoinduced Interfacial Proton Coupled Electron Transfer from CdSe Quantum Dots to 4,4′-Bipyridine
journal, January 2016

  • Chen, Jinquan; Wu, Kaifeng; Rudshteyn, Benjamin
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b10354

Coupled electron transfers in artificial photosynthesis
journal, October 2007

  • Hammarström, Leif; Styring, Stenbjörn
  • Philosophical Transactions of the Royal Society B: Biological Sciences, Vol. 363, Issue 1494
  • DOI: 10.1098/rstb.2007.2225

Exciton Dynamics and Biexciton Formation in Single-Walled Carbon Nanotubes Studied with Femtosecond Transient Absorption Spectroscopy
journal, March 2008

  • Styers-Barnett, David J.; Ellison, Stephen P.; Mehl, Brian P.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 12
  • DOI: 10.1021/jp7099256

Concerted Proton−Electron Transfer in the Oxidation of Hydrogen-Bonded Phenols
journal, April 2006

  • Rhile, Ian J.; Markle, Todd F.; Nagao, Hirotaka
  • Journal of the American Chemical Society, Vol. 128, Issue 18, 6075-6088
  • DOI: 10.1021/ja054167

Quantum coherence in photosynthesis for efficient solar-energy conversion
journal, July 2014

  • Romero, Elisabet; Augulis, Ramunas; Novoderezhkin, Vladimir I.
  • Nature Physics, Vol. 10, Issue 9
  • DOI: 10.1038/nphys3017

The role of proton coupled electron transfer in water oxidation
journal, January 2012

  • Gagliardi, Christopher J.; Vannucci, Aaron K.; Concepcion, Javier J.
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee03311a

Biochemistry and Theory of Proton-Coupled Electron Transfer
journal, January 2014

  • Migliore, Agostino; Polizzi, Nicholas F.; Therien, Michael J.
  • Chemical Reviews, Vol. 114, Issue 7
  • DOI: 10.1021/cr4006654

Marcus-type driving force correlations reveal the mechanism of proton-coupled electron transfer for phenols and [Ru(bpy) 3 ] 3+ in water at low pH
journal, January 2016

  • Soetbeer, Janne; Dongare, Prateek; Hammarström, Leif
  • Chemical Science, Vol. 7, Issue 7
  • DOI: 10.1039/C6SC00597G

Photoinduced PCET in Ruthenium–Phenol Systems: Thermodynamic Equivalence of Uni- and Bidirectional Reactions
journal, March 2015

Integrating proton coupled electron transfer (PCET) and excited states
journal, November 2010

  • Gagliardi, Christopher J.; Westlake, Brittany C.; Kent, Caleb A.
  • Coordination Chemistry Reviews, Vol. 254, Issue 21-22
  • DOI: 10.1016/j.ccr.2010.03.001

Mimicking Electron Transfer Reactions in Photosystem II:  Synthesis and Photochemical Characterization of a Ruthenium(II) Tris(bipyridyl) Complex with a Covalently Linked Tyrosine
journal, November 1997

  • Magnuson, Ann; Berglund, Helena; Korall, Peter
  • Journal of the American Chemical Society, Vol. 119, Issue 44
  • DOI: 10.1021/ja972161h

Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work
journal, November 2014

Role of Solvent Dynamics in Photoinduced Proton-Coupled Electron Transfer in a Phenol–Amine Complex in Solution
journal, August 2015

Proton coupled electron transfer from the excited state of a ruthenium( ii ) pyridylimidazole complex
journal, January 2016

  • Pannwitz, Andrea; Wenger, Oliver S.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C6CP00437G

Large Molecular Quadratic Hyperpolarizabilities in Donor/Acceptor-Substituted trans -Tetraammineruthenium(II) Complexes
journal, July 1997

  • Coe, Benjamin J.; Chamberlain, Michelle C.; Essex-Lopresti, Jonathan P.
  • Inorganic Chemistry, Vol. 36, Issue 15
  • DOI: 10.1021/ic961465m
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