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

Title: Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites

Abstract

The bimolecular rate coefficients ($$k_q^{obs}$$) for quenching the metal-to-ligand charge transfer excited states of two Ru polypyridine complexes containing H-bond accepting sites by six p-substituted phenols exhibit abrupt deviations from the expected linear correlations of log$$k_q^{obs}$$ with phenol’s Hammett σp constant. This pattern is attributed to a transition of the quenching mechanism from a concerted electron-proton transfer (EPT) to a proton transfer (PT); the latter becomes predominant for the most acidic phenols in MeCN, but not in CH2Cl2. This assertion is supported by a detailed thermochemical analysis, which also excludes the quenching pathways involving electron transfer from phenols with or without deprotonation of phenols to the solvent, either concerted or sequential. The transition from EPT to PT upon the σp increase is consistent/supported by the magnitudes of the measured and computed PhOH/OD kinetic isotope effects and by the observed reduction of the EPT product yields upon replacing the low σp methoxyphenol by the high σp nitrophenol. In addition to modulating the relative contribution of the EPT and PT quenching pathways, the solvent strongly affects the bimolecular rate coefficients for the EPT quenching proper. Unlike with H-atom transfer reactions, this kinetic solvent effect could not be quantitatively accounted for by the phenol-solvent H-bonding alone, which suggests a solvent effect on the H-bonding constants in the phenol-Ru complex precursor exciplexes and/or on the unimolecular EPT rate coefficients within these exciplexes.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1483559
Alternate Identifier(s):
OSTI ID: 1479827
Report Number(s):
BNL-209492-2018-JAAM
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 44; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Lymar, Sergei V., Ertem, Mehmed Z., and Polyansky, Dmitry E. Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites. United States: N. p., 2018. Web. doi:10.1039/C8DT03858A.
Lymar, Sergei V., Ertem, Mehmed Z., & Polyansky, Dmitry E. Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites. United States. doi:10.1039/C8DT03858A.
Lymar, Sergei V., Ertem, Mehmed Z., and Polyansky, Dmitry E. Fri . "Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites". United States. doi:10.1039/C8DT03858A. https://www.osti.gov/servlets/purl/1483559.
@article{osti_1483559,
title = {Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites},
author = {Lymar, Sergei V. and Ertem, Mehmed Z. and Polyansky, Dmitry E.},
abstractNote = {The bimolecular rate coefficients ($k_q^{obs}$) for quenching the metal-to-ligand charge transfer excited states of two Ru polypyridine complexes containing H-bond accepting sites by six p-substituted phenols exhibit abrupt deviations from the expected linear correlations of log$k_q^{obs}$ with phenol’s Hammett σp constant. This pattern is attributed to a transition of the quenching mechanism from a concerted electron-proton transfer (EPT) to a proton transfer (PT); the latter becomes predominant for the most acidic phenols in MeCN, but not in CH2Cl2. This assertion is supported by a detailed thermochemical analysis, which also excludes the quenching pathways involving electron transfer from phenols with or without deprotonation of phenols to the solvent, either concerted or sequential. The transition from EPT to PT upon the σp increase is consistent/supported by the magnitudes of the measured and computed PhOH/OD kinetic isotope effects and by the observed reduction of the EPT product yields upon replacing the low σp methoxyphenol by the high σp nitrophenol. In addition to modulating the relative contribution of the EPT and PT quenching pathways, the solvent strongly affects the bimolecular rate coefficients for the EPT quenching proper. Unlike with H-atom transfer reactions, this kinetic solvent effect could not be quantitatively accounted for by the phenol-solvent H-bonding alone, which suggests a solvent effect on the H-bonding constants in the phenol-Ru complex precursor exciplexes and/or on the unimolecular EPT rate coefficients within these exciplexes.},
doi = {10.1039/C8DT03858A},
journal = {Dalton Transactions},
number = 44,
volume = 47,
place = {United States},
year = {2018},
month = {10}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

Chart 1 Chart 1: Ruthenium complexes containing the proton-accepting, uncoordinated, ligand’s N sites investigated in this work (bpy = 2,2′-bipyridine; pbn = 2-(2-pyridyl)benzo[b]-1,5-naphthyridine; bpz = 2,2′-bipyrazine).

Save / Share:

Works referenced in this record:

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities
journal, May 2016

  • Miller, David C.; Tarantino, Kyle T.; Knowles, Robert R.
  • Topics in Current Chemistry, Vol. 374, Issue 3
  • DOI: 10.1007/s41061-016-0030-6

The Minnesota Density Functionals and their Applications to Problems in Mineralogy and Geochemistry
journal, January 2010

  • Zhao, Y.; Truhlar, D. G.
  • Reviews in Mineralogy and Geochemistry, Vol. 71, Issue 1
  • DOI: 10.2138/rmg.2010.71.2

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

Density Functionals with Broad Applicability in Chemistry
journal, February 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Accounts of Chemical Research, Vol. 41, Issue 2
  • DOI: 10.1021/ar700111a

Reaction of tert-butoxy radicals with phenols. Comparison with the reactions of carbonyl triplets
journal, July 1981

  • Das, P. K.; Encinas, M. V.; Steenken, S.
  • Journal of the American Chemical Society, Vol. 103, Issue 14
  • DOI: 10.1021/ja00404a030

Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production
journal, April 2012

  • Horvath, S.; Fernandez, L. E.; Soudackov, A. V.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1118333109

Über HD-isotopeneffekte bei wasserstoffbrücken zwischen alkoholen und tertiären aminen
journal, January 1969


Analysis of Kinetic Isotope Effects for Proton-Coupled Electron Transfer Reactions
journal, March 2009

  • Edwards, Sarah J.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon
  • The Journal of Physical Chemistry A, Vol. 113, Issue 10
  • DOI: 10.1021/jp809122y

Photoinduced Proton-Coupled Electron Transfers in Biorelevant Phenolic Systems
journal, October 2011


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

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD + Model Ligand: Pulse and Steady-State Radiolysis Studies
journal, May 2008

  • Polyansky, Dmitry E.; Cabelli, Diane; Muckerman, James T.
  • Inorganic Chemistry, Vol. 47, Issue 10
  • DOI: 10.1021/ic702139n

Recent Experimental Advances on Excited-State Intramolecular Proton Coupled Electron Transfer Reaction
journal, October 2010

  • Hsieh, Cheng-Chih; Jiang, Chang-Ming; Chou, Pi-Tai
  • Accounts of Chemical Research, Vol. 43, Issue 10
  • DOI: 10.1021/ar1000499

Proton-coupled electron transfer with photoexcited ruthenium(II), rhenium(I), and iridium(III) complexes
journal, January 2015


Proton-Coupled Electron-Transfer Reactions at a Distance in DNA Duplexes:  Kinetic Deuterium Isotope Effect
journal, September 2001

  • Shafirovich, Vladimir; Dourandin, Alexander; Geacintov, Nicholas E.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 35
  • DOI: 10.1021/jp0044734

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

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

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 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

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

Proton-Coupled Electron Transfer in Artificial Photosynthetic Systems
journal, January 2018


Abnormal Solvent Effects on Hydrogen Atom Abstraction. 3. Novel Kinetics in Sequential Proton Loss Electron Transfer Chemistry
journal, October 2005

  • Litwinienko, Grzegorz; Ingold, K. U.
  • The Journal of Organic Chemistry, Vol. 70, Issue 22
  • DOI: 10.1021/jo051474p

Proton-Coupled Electron-Transfer Oxidation of Phenols by Hexachloroiridate(IV)
journal, December 2008

  • Song, Na; Stanbury, David M.
  • Inorganic Chemistry, Vol. 47, Issue 24
  • DOI: 10.1021/ic8015595

Concerted proton–electron transfers in the oxidation of phenols
journal, January 2010

  • Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 37
  • DOI: 10.1039/c0cp00063a

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

Role of Hydrogen Bonding in Photoinduced Electron–Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand
journal, August 2017

  • Lymar, Sergei V.; Ertem, Mehmed Z.; Lewandowska-Andralojc, Anna
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
  • DOI: 10.1021/acs.jpclett.7b01614

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

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

FT-IR (7500−1800 cm -1 ) Study of Hydrogen-Bond Complexes between Phenols−OH(OD) and Pyridine. Evidence of Proton Transfer in the Second Vibrational Excited State
journal, November 1997

  • Rospenk, Maria; Zeegers-Huyskens, Thérèse
  • The Journal of Physical Chemistry A, Vol. 101, Issue 45
  • DOI: 10.1021/jp971859e

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

Reversible Hydride Generation and Release from the Ligand of [Ru(pbn)(bpy)2](PF6)2 Driven by a pbn-Localized Redox Reaction
journal, September 2005

  • Koizumi, Take-aki; Tanaka, Koji
  • Angewandte Chemie International Edition, Vol. 44, Issue 36
  • DOI: 10.1002/anie.200500760

Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II
journal, April 2017


Proton-Coupled Photoinduced Electron Transfer, Deuterium Isotope Effects, and Fluorescence Quenching in Noncovalent Benzo[a]pyrenetetraol-Nucleoside Complexes in Aqueous Solutions
journal, May 1995

  • Shafirovich, Vladimir Ya.; Courtney, Scott H.; Ya, Naiqi
  • Journal of the American Chemical Society, Vol. 117, Issue 17
  • DOI: 10.1021/ja00122a024

Theoretical studies of proton-coupled electron transfer: Models and concepts relevant to bioenergetics
journal, February 2008

  • Hammesschiffer, S.; Hatcher, E.; Ishikita, H.
  • Coordination Chemistry Reviews, Vol. 252, Issue 3-4
  • DOI: 10.1016/j.ccr.2007.07.019

Protonation equilibria in excited-state tris(bipyrazine)ruthenium(II)
journal, March 1983

  • Crutchley, R. J.; Kress, N.; Lever, A. B. P.
  • Journal of the American Chemical Society, Vol. 105, Issue 5
  • DOI: 10.1021/ja00343a016

Ionic Association. III. The Equilibrium between Ion Pairs and Free Ions
journal, October 1958

  • Fuoss, Raymond M.
  • Journal of the American Chemical Society, Vol. 80, Issue 19
  • DOI: 10.1021/ja01552a016

Photochemical and Radiolytic Production of an Organic Hydride Donor with a RuII Complex Containing an NAD+ Model Ligand
journal, May 2007

  • Polyansky, Dmitry; Cabelli, Diane; Muckerman, James T.
  • Angewandte Chemie International Edition, Vol. 46, Issue 22
  • DOI: 10.1002/anie.200700304

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

Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer
journal, June 2011

  • Auer, Benjamin; Fernandez, Laura E.; Hammes-Schiffer, Sharon
  • Journal of the American Chemical Society, Vol. 133, Issue 21
  • DOI: 10.1021/ja201560v

Deuterium Isotope Effects on Hydrogen Bonding
journal, November 1966

  • Singh, Surjit; Rao, C. N. R.
  • Canadian Journal of Chemistry, Vol. 44, Issue 22
  • DOI: 10.1139/v66-393

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


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

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

Kinetic deuterium isotope effect and hydrogen bonding
journal, January 1975


Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990

  • Andrae, D.; H�u�ermann, U.; Dolg, M.
  • Theoretica Chimica Acta, Vol. 77, Issue 2
  • DOI: 10.1007/BF01114537

Kinetic Isotope Effect and Extended pH-Dependent Studies of the Oxidation of Hydroxylamine by Hexachloroiridate(IV):  ET and PCET
journal, June 2007

  • Makarycheva-Mikhailova, Anastasia V.; Stanbury, David M.; McKee, Michael L.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 24
  • DOI: 10.1021/jp068990j

Reactivity of the copper( iii )-hydroxide unit with phenols
journal, January 2017

  • Dhar, Debanjan; Yee, Gereon M.; Markle, Todd F.
  • Chemical Science, Vol. 8, Issue 2
  • DOI: 10.1039/C6SC03039D

Derivation of rate expressions for nonadiabatic proton-coupled electron transfer reactions in solution
journal, August 2000

  • Soudackov, Alexander; Hammes-Schiffer, Sharon
  • The Journal of Chemical Physics, Vol. 113, Issue 6
  • DOI: 10.1063/1.482053

Calorimetric and spectrophotometric comparison of adducts of phenol and deuteriophenol
journal, February 1974

  • Boettcher, John W.; Drago, Russell S.
  • The Journal of Physical Chemistry, Vol. 78, Issue 4
  • DOI: 10.1021/j100597a023

Proton-coupled electron transfer in the oxidation of guanines by an aromatic pyrenyl radical cation in aqueous solutions
journal, January 2000

  • Kuzmin, Vladimir A.; Dourandin, Alexander; Shafirovich, Vladimir
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 7
  • DOI: 10.1039/b000212g

Redox properties of ruthenium(II) tris chelate complexes containing the ligands 2,2'-bipyrazine, 2,2'-bipyridine, and 2,2'-bipyrimidine
journal, May 1983

  • Rillema, D. Paul; Allen, G.; Meyer, T. J.
  • Inorganic Chemistry, Vol. 22, Issue 11
  • DOI: 10.1021/ic00153a012

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

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


Determination of the equilibrium constant of hydrogen bonding between substituted h-[d]-phenols and vinyl acetate in CCl4 by i.r. measurements
journal, January 1976

  • Simonyi, M.; Kovács, I.; Kardos, J.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 32, Issue 7
  • DOI: 10.1016/0584-8539(76)80187-0