Excited-state proton-coupled electron transfer within ion pairs.

Chemical Science
Wesley B SwordsLeif Hammarström

Abstract

The use of light to drive proton-coupled electron transfer (PCET) reactions has received growing interest, with recent focus on the direct use of excited states in PCET reactions (ES-PCET). Electrostatic ion pairs provide a scaffold to reduce reaction orders and have facilitated many discoveries in electron-transfer chemistry. Their use, however, has not translated to PCET. Herein, we show that ion pairs, formed solely through electrostatic interactions, provide a general, facile means to study an ES-PCET mechanism. These ion pairs formed readily between salicylate anions and tetracationic ruthenium complexes in acetonitrile solution. Upon light excitation, quenching of the ruthenium excited state occurred through ES-PCET oxidation of salicylate within the ion pair. Transient absorption spectroscopy identified the reduced ruthenium complex and oxidized salicylate radical as the primary photoproducts of this reaction. The reduced reaction order due to ion pairing allowed the first-order PCET rate constants to be directly measured through nanosecond photoluminescence spectroscopy. These PCET rate constants saturated at larger driving forces consistent with approaching the Marcus barrierless region. Surprisingly, a proton-transfer...Continue Reading

References

Oct 28, 1998·Proceedings of the National Academy of Sciences of the United States of America·J JortnerM E Michel-Beyerle
Dec 15, 2000·Biochimica Et Biophysica Acta·H A ChuG T Babcock
Oct 23, 1996·Inorganic Chemistry·Mark RuthkoskyGerald J. Meyer
Mar 18, 2005·Journal of the American Chemical Society·Martin SjödinLeif Hammarström
Jun 30, 2005·Journal of the American Chemical Society·Steven Y Reece, Daniel G Nocera
Jan 5, 2006·Inorganic Chemistry·Andras MartonGerald J Meyer
May 4, 2006·Journal of the American Chemical Society·Ian J RhileJames M Mayer
Oct 5, 2006·Journal of the American Chemical Society·Martin SjödinLeif Hammarström
Oct 18, 2006·Proceedings of the National Academy of Sciences of the United States of America·Nathan S Lewis, Daniel G Nocera
Nov 15, 2007·Chemical Reviews·My Hang V Huynh, Thomas J Meyer
Nov 22, 2007·Journal of the American Chemical Society·Tania IreboLeif Hammarström
Dec 15, 2007·Angewandte Chemie·Todd F Markle, James M Mayer
Jan 24, 2008·Proceedings of the National Academy of Sciences of the United States of America·Todd F MarkleJames M Mayer
Jun 28, 2008·Journal of the American Chemical Society·Tania IreboLeif Hammarström
Sep 20, 2008·Chemical Communications : Chem Comm·Jonathan C FreysOliver S Wenger
Apr 7, 2009·Annual Review of Biochemistry·Steven Y Reece, Daniel G Nocera
Jun 6, 2009·Journal of the American Chemical Society·Elizabeth R YoungDaniel G Nocera
Oct 14, 2009·Proceedings of the National Academy of Sciences of the United States of America·Cyrille CostentinJean-Michel Savéant
Oct 24, 2009·Journal of the American Chemical Society·James M GardnerGerald J Meyer
Nov 12, 2009·Accounts of Chemical Research·Devens GustAna L Moore
Nov 6, 2010·Chemical Reviews·Sharon Hammes-Schiffer, Alexei A Stuchebrukhov
Aug 5, 2011·Journal of the American Chemical Society·Ming-Tian ZhangLeif Hammarström
Oct 28, 2011·Accounts of Chemical Research·Julien BoninCédric Tard
May 9, 2012·Proceedings of the National Academy of Sciences of the United States of America·Byron H FarnumGerald J Meyer
Jun 19, 2012·Chemical Reviews·David R WeinbergThomas J Meyer
Feb 14, 2013·Accounts of Chemical Research·Oliver S Wenger
Mar 16, 2013·The Journal of Physical Chemistry Letters·Jeffrey J WarrenJames M Mayer
Jul 22, 2014·Journal of the American Chemical Society·Thomas T Eisenhart, Jillian L Dempsey
Jan 24, 2015·Nature Chemistry·Marc BourrezLeif Hammarström
Dec 15, 2015·Angewandte Chemie·Martin Kuss-Petermann, Oliver S Wenger
Apr 21, 2016·Physical Chemistry Chemical Physics : PCCP·Andrea Pannwitz, Oliver S Wenger
Jul 30, 2016·Accounts of Chemical Research·Emily C Gentry, Robert R Knowles
Aug 9, 2016·The Journal of Physical Chemistry. B·Thomas T EisenhartJillian L Dempsey
Dec 16, 2016·Journal of the American Chemical Society·Ludovic Troian-GautierGerald J Meyer
Aug 31, 2017·Journal of the American Chemical Society·Sara A M WehlinGerald J Meyer

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Citations

Apr 7, 2021·The Journal of Organic Chemistry·Dhananjay YadavMaya Shankar Singh
Nov 27, 2020·The Journal of Physical Chemistry. B·Ananta DeyHirendra N Ghosh
Jan 7, 2021·Journal of the American Chemical Society·Robin TyburskiLeif Hammarström

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Methods Mentioned

BETA
PCET
nuclear magnetic resonance

Software Mentioned

Edinburgh
LKS60
L900
CEPT
OriginPro

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