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Title: Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand

Abstract

Electron-proton transfer, EPT, from phenols to a triplet MLCT-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to an inconsistent data analysis. In conclusion, control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
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  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1376190
Report Number(s):
BNL-114182-2017-JA
Journal ID: ISSN 1948-7185; R&D Project: CO037; KC0304030
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lymar, Sergei V., Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, and Polyansky, Dmitry E. Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01614.
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Lymar, Sergei V., Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, & Polyansky, Dmitry E. Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand. United States. https://doi.org/10.1021/acs.jpclett.7b01614
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Lymar, Sergei V., Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, and Polyansky, Dmitry E. Wed . "Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand". United States. https://doi.org/10.1021/acs.jpclett.7b01614. https://www.osti.gov/servlets/purl/1376190.
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@article{osti_1376190,
title = {Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand},
author = {Lymar, Sergei V. and Ertem, Mehmed Z. and Lewandowska-Andralojc, Anna and Polyansky, Dmitry E.},
abstractNote = {Electron-proton transfer, EPT, from phenols to a triplet MLCT-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to an inconsistent data analysis. In conclusion, control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.},
doi = {10.1021/acs.jpclett.7b01614},
journal = {Journal of Physical Chemistry Letters},
number = ,
volume = 8,
place = {United States},
year = {Wed Aug 09 00:00:00 EDT 2017},
month = {Wed Aug 09 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acs.jpclett.7b01614
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Works referenced in this record:

Proton-Coupled Electron Transfer
journal, November 2007

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

Models for Proton-coupled Electron Transfer in Photosystem II
journal, January 2006

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

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

Theory of Coupled Electron and Proton Transfer Reactions
journal, December 2010

  • Hammes-Schiffer, Sharon; Stuchebrukhov, Alexei A.
  • Chemical Reviews, Vol. 110, Issue 12
  • DOI: 10.1021/cr1001436

Excited-State Proton-Coupled Electron Transfer: Different Avenues for Promoting Proton/Electron Movement with Solar Photons
journal, April 2017

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

Chemical Approaches to Artificial Photosynthesis. 2
journal, October 2005

  • Alstrum-Acevedo, James H.; Brennaman, M. Kyle; Meyer, Thomas J.
  • Inorganic Chemistry, Vol. 44, Issue 20
  • DOI: 10.1021/ic050904r

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

Effects of Protonation State on a Tyrosine−Histidine Bioinspired Redox Mediator †
journal, November 2010

  • Moore, Gary F.; Hambourger, Michael; Kodis, Gerdenis
  • The Journal of Physical Chemistry B, Vol. 114, Issue 45
  • DOI: 10.1021/jp101592m

Proton-Coupled Electron Transfer in Azobenzene/Hydrazobenzene Couples with Pendant Acid–Base Functions. Hydrogen-Bonding and Structural Effects
journal, June 2014

  • Savéant, Jean-Michel; Tard, Cédric
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja504484a

Water (in Water) as an Intrinsically Efficient Proton Acceptor in Concerted Proton Electron Transfers
journal, May 2011

  • Bonin, Julien; Costentin, Cyrille; Louault, Cyril
  • Journal of the American Chemical Society, Vol. 133, Issue 17
  • DOI: 10.1021/ja110935c

Concerted Electron–Proton Transfer (EPT) in the Oxidation of Tryptophan with Hydroxide as a Base
journal, December 2011

  • Gagliardi, Christopher J.; Binstead, Robert A.; Thorp, H. Holden
  • Journal of the American Chemical Society, Vol. 133, Issue 49
  • DOI: 10.1021/ja207379n

Comparing the Hydrogen-Bonding Effect of Brönsted Bases in Solution and When They Are Covalently Bound to the Surface of Glassy Carbon Electrodes in the Electrochemical Behavior of Hydroquinone
journal, September 2012

  • Medina-Ramos, Jonnathan; Alligrant, Timothy M.; Clingenpeel, Amy
  • The Journal of Physical Chemistry C, Vol. 116, Issue 38
  • DOI: 10.1021/jp306542y

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

Kinetic Isotope Effects in Reductive Excited-State Quenching of Ru(2,2′-bipyrazine) 3 2+ by Phenols
journal, December 2011

  • Bronner, Catherine; Wenger, Oliver S.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 1
  • DOI: 10.1021/jz201494n

Structural and pH Dependence of Excited State PCET Reactions Involving Reductive Quenching of the MLCT Excited State of [Ru II (bpy) 2 (bpz)] 2+ by Hydroquinones
journal, April 2011

  • Lebedeva, Natalia V.; Schmidt, Robert D.; Concepcion, Javier J.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 15
  • DOI: 10.1021/jp200381n

Distance Dependence of Bidirectional Concerted Proton-Electron Transfer in Phenol-Ru(2,2′-bipyridine) 3 2+ Dyads
journal, February 2014

  • Chen, Jing; Kuss-Petermann, Martin; Wenger, Oliver S.
  • Chemistry - A European Journal, Vol. 20, Issue 14
  • DOI: 10.1002/chem.201304256

Photoacid Behavior versus Proton-Coupled Electron Transfer in Phenol–Ru(bpy) 3 2+ Dyads
journal, July 2013

  • Kuss-Petermann, Martin; Wenger, Oliver S.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 28
  • DOI: 10.1021/jp402567m

Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer
journal, January 2012

  • Pizano, Arturo A.; Yang, Jay L.; Nocera, Daniel G.
  • Chemical Science, Vol. 3, Issue 8
  • DOI: 10.1039/c2sc20113e

Electron Transfer Studies of Ruthenium(II) Complexes with Biologically Important Phenolic Acids and Tyrosine
journal, December 2015

  • Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian
  • Journal of Fluorescence, Vol. 26, Issue 2
  • DOI: 10.1007/s10895-015-1738-3

Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids
journal, July 2016

  • Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian
  • Journal of Molecular Structure, Vol. 1115
  • DOI: 10.1016/j.molstruc.2016.02.088

Analysis of Hydrogen-Bonding Effects on Excited-State Proton-Coupled Electron Transfer from a Series of Phenols to a Re(I) Polypyridyl Complex
journal, June 2017

  • Dongare, Prateek; Bonn, Annabell G.; Maji, Somnath
  • The Journal of Physical Chemistry C, Vol. 121, Issue 23
  • DOI: 10.1021/acs.jpcc.7b02449

Kinetic Solvent Effects on Hydrogen-Atom Abstractions:  Reliable, Quantitative Predictions via a Single Empirical Equation 1
journal, January 2001

  • Snelgrove, Darren W.; Lusztyk, Janusz; Banks, J. T.
  • Journal of the American Chemical Society, Vol. 123, Issue 3
  • DOI: 10.1021/ja002301e

Effects of Solvation on the Enthalpies of Reaction of tert-Butoxyl Radicals with Phenol and on the Calculated O-H Bond Strength in Phenol
journal, August 1995

  • Wayner, D. D. M.; Lusztyk, E.; Page, D.
  • Journal of the American Chemical Society, Vol. 117, Issue 34
  • DOI: 10.1021/ja00139a006

Abnormal Solvent Effects on Hydrogen Atom Abstractions. 1. The Reactions of Phenols with 2,2-Diphenyl-1-picrylhydrazyl (dpph • ) in Alcohols
journal, May 2003

  • Litwinienko, Grzegorz; Ingold, K. U.
  • The Journal of Organic Chemistry, Vol. 68, Issue 9
  • DOI: 10.1021/jo026917t

Critical Re-evaluation of the O−H Bond Dissociation Enthalpy in Phenol
journal, March 2005

  • Mulder, Peter; Korth, Hans-Gert; Pratt, Derek A.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 11
  • DOI: 10.1021/jp047148f

Solvent Effects on the Rates and Mechanisms of Reaction of Phenols with Free Radicals
journal, March 2007

  • Litwinienko, Grzegorz; Ingold, K. U.
  • Accounts of Chemical Research, Vol. 40, Issue 3
  • DOI: 10.1021/ar0682029

Kinetic Solvent Effects on the Reaction of an Aromatic Ketone π,π* Triplet with Phenol. Rate-Retarding and Rate-Accelerating Effects of Hydrogen-Bond Acceptor Solvents
journal, August 2007

  • Galian, Raquel E.; Litwinienko, Grzegorz; Pérez-Prieto, Julia
  • Journal of the American Chemical Society, Vol. 129, Issue 30
  • DOI: 10.1021/ja071716y

Hydrogen bonding. Part 7. A scale of solute hydrogen-bond acidity based on log K values for complexation in tetrachloromethane
journal, January 1989

  • Abraham, Michael H.; Grellier, Priscilla L.; Prior, David V.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 6
  • DOI: 10.1039/p29890000699

Hydrogen bonding. Part 10. A scale of solute hydrogen-bond basicity using log K values for complexation in tetrachloromethane
journal, January 1990

  • Abraham, Michael H.; Grellier, Priscilla L.; Prior, David V.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 4
  • DOI: 10.1039/p29900000521

Scales of solute hydrogen-bonding: their construction and application to physicochemical and biochemical processes
journal, January 1993

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    Works referencing / citing this record:

    Unraveling the Mechanisms of the Excited‐State Intermolecular Proton Transfer (ESPT) for a D‐π‐A Molecular Architecture
    journal, June 2019

    • Hong, Dan‐Li; Luo, Yang‐Hui; He, Xiao‐Tong
    • Chemistry – A European Journal
    • DOI: 10.1002/chem.201900856
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