Electronic and structural elements that regulate the excited-state dynamics in purine nucleobase derivatives

Journal of the American Chemical Society
Carlos E Crespo-HernándezInés Corral

Abstract

The excited-state dynamics of the purine free base and 9-methylpurine are investigated using experimental and theoretical methods. Femtosecond broadband transient absorption experiments reveal that excitation of these purine derivatives in aqueous solution at 266 nm results primarily in ultrafast conversion of the S2(ππ*) state to the vibrationally excited (1)nπ* state. Following vibrational and conformational relaxation, the (1)nπ* state acts as a doorway state in the efficient population of the triplet manifold with an intersystem crossing lifetime of hundreds of picoseconds. Experiments show an almost 2-fold increase in the intersystem crossing rate on going from polar aprotic to nonpolar solvents, suggesting that a solvent-dependent energy barrier must be surmounted to access the singlet-to-triplet crossing region. Ab initio static and surface-hopping dynamics simulations lend strong support to the proposed relaxation mechanism. Collectively, the experimental and computational results demonstrate that the accessibility of the nπ* states and the topology of the potential energy surfaces in the vicinity of conical intersections are key elements in controlling the excited-state dynamics of the purine derivatives. From a struct...Continue Reading

References

Nov 1, 1996·Photochemistry and Photobiology·D H MurgidaR Erra-Balsells
Oct 18, 2001·Journal of the American Chemical Society·J M PecourtB Kohler
Apr 15, 2004·Chemical Reviews·Carlos E Crespo-HernándezBern Kohler
Feb 11, 2005·Journal of the American Chemical Society·Manuela MerchánLluís Blancafort
Apr 20, 2005·The Journal of Chemical Physics·Christel M Marian
Apr 28, 2005·Journal of the American Chemical Society·Serhiy PerunWolfgang Domcke
May 6, 2006·The Journal of Chemical Physics·Hui Chen, Shuhua Li
May 30, 2006·Proceedings of the National Academy of Sciences of the United States of America·Luis Serrano-AndrésAntonio C Borin
Jun 22, 2006·Chemistry : a European Journal·Luis Serrano-AndrésAntonio Carlos Borin
Jan 2, 2007·Proceedings of the National Academy of Sciences of the United States of America·Patrick M HareBern Kohler
Feb 6, 2007·The Journal of Physical Chemistry. a·Christel M Marian
May 24, 2007·Chemical Communications : Chem Comm·Susan QuinnJohn M Kelly
Oct 12, 2007·The Journal of Physical Chemistry. B·Juan José Serrano-PérezLuis Serrano-Andrés
Jan 25, 2008·Journal of the American Chemical Society·Luis Serrano-AndrésAntonio Carlos Borin
Mar 14, 2008·Journal of the American Chemical Society·Wai-Ming KwokDavid Lee Phillips
May 1, 2008·Journal of the American Chemical Society·Mario Barbatti, Hans Lischka
Oct 31, 2008·The Journal of Physical Chemistry. a·Shohei YamazakiAndrzej L Sobolewski
Nov 7, 2008·The Journal of Physical Chemistry. a·Elizabeth Mburu, Spiridoula Matsika
Nov 18, 2008·Annual Review of Physical Chemistry·Chris T MiddletonBern Kohler
Feb 17, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Michael SchneiderIngo Fischer
Apr 28, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Zhenggang LanWalter Thiel
Aug 13, 2009·The Journal of Physical Chemistry. a·Mihajlo EtinskiChristel M Marian
Sep 29, 2009·The Journal of Physical Chemistry. B·Roberto ImprotaFabrizio Santoro
Oct 30, 2009·Physical Chemistry Chemical Physics : PCCP·Shohei YamazakiWolfgang Domcke
Jan 21, 2010·The Journal of Physical Chemistry. a·Francois-Alexandre MiannayDimitra Markovitsi
Apr 2, 2010·Physical Chemistry Chemical Physics : PCCP·Walid Mohamed Ibrahim HassanYuichi Fujimura
Apr 22, 2010·Physical Chemistry Chemical Physics : PCCP·Vassil B DelchevWolfgang Domcke
Dec 1, 2010·Proceedings of the National Academy of Sciences of the United States of America·Mario BarbattiHans Lischka
Jan 12, 2011·The Journal of Chemical Physics·Mario BarbattiHans Lischka
Jun 11, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Gerald RyseckPeter Gilch
Nov 11, 2011·Accounts of Chemical Research·Guang-Jiu Zhao, Ke-Li Han
Apr 11, 2012·Journal of the American Chemical Society·Juan P Villabona-MonsalveJorge Peón
May 10, 2012·Physical Chemistry Chemical Physics : PCCP·Berit HeggenWalter Thiel
Jul 4, 2012·Physical Chemistry Chemical Physics : PCCP·Jinquan Chen, Bern Kohler
Dec 20, 2012·The Journal of Chemical Physics·Mario BarbattiWalter Thiel
Jan 19, 2013·The Journal of Physical Chemistry. a·Juan P Villabona-MonsalveJorge Peón
Mar 27, 2013·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Christian ReichardtCarlos E Crespo-Hernández
Mar 30, 2013·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Chopen Chan-Wut ChengWai-Ming Kwok
Apr 26, 2013·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Thomas GustavssonRoberto Improta
Jun 8, 2013·Physical Chemistry Chemical Physics : PCCP·Franziska BuchnerAndrea Lübcke

❮ Previous
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Citations

Aug 19, 2015·The Journal of Physical Chemistry. a·Sebastian MaiLeticia González
Oct 7, 2015·The Journal of Physical Chemistry. a·Sermsiri ChaiwongwattanaNađa Došlić
Nov 6, 2015·The Journal of Physical Chemistry Letters·Matthew M Brister, Carlos E Crespo-Hernández
May 10, 2017·Physical Chemistry Chemical Physics : PCCP·R M DiScipioC E Crespo-Hernández
Feb 9, 2017·Physical Chemistry Chemical Physics : PCCP·Antonio Carlos BorinLeticia González
Jun 28, 2017·The Journal of Physical Chemistry. a·Faady M SiouriMattanjah S de Vries
Oct 7, 2015·Physical Chemistry Chemical Physics : PCCP·M PollumC E Crespo-Hernández
Jul 21, 2017·Physical Chemistry Chemical Physics : PCCP·Sayan Mondal, Mrinalini Puranik
Jan 21, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Katharina RöttgerFriedrich Temps
Jan 27, 2018·Faraday Discussions·Brennan AshwoodCarlos E Crespo-Hernández
Mar 1, 2018·Annual Review of Physical Chemistry·Juan J Nogueira, Leticia González
Feb 24, 2016·Physical Chemistry Chemical Physics : PCCP·M M BristerC E Crespo-Hernández
May 6, 2016·Physical Chemistry Chemical Physics : PCCP·Sayan Mondal, Mrinalini Puranik
Aug 20, 2016·Physical Chemistry Chemical Physics : PCCP·A B StephansenT I Sølling
Jun 20, 2018·Physical Chemistry Chemical Physics : PCCP·Victor M FreixasDmitrii Shalashilin
Jul 7, 2018·Photochemistry and Photobiology·Brennan AshwoodCarlos E Crespo-Hernández
Oct 6, 2016·Nature Communications·Sebastian MaiLeticia González
Feb 1, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Zhongneng ZhouJianhua Xu
Jun 13, 2019·Physical Chemistry Chemical Physics : PCCP·Lara Martínez-FernándezInés Corral
Oct 10, 2019·Physical Chemistry Chemical Physics : PCCP·Marin SapunarNađa Došlić
Dec 8, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Konrad SkotnickiKrzysztof Bobrowski
Nov 20, 2018·Wiley Interdisciplinary Reviews. Computational Molecular Science·Sebastian MaiLeticia González
Jan 1, 2021·The Journal of Chemical Physics·Aliya MukazhanovaSahar Sharifzadeh
Feb 21, 2021·The Journal of Chemical Physics·Sarah E KrulCarlos E Crespo-Hernández
Feb 10, 2021·Annual Review of Physical Chemistry·Saikat MukherjeeSergey A Varganov
Apr 21, 2021·Physical Chemistry Chemical Physics : PCCP·Leila ShahrokhGholamhassan Azimi
May 7, 2021·Chemical Society Reviews·Dmytro DziubaYves Mély
Jan 26, 2018·The Journal of Physical Chemistry. a·Kilian R A SchneiderBenjamin Dietzek
Mar 21, 2018·Chemical Reviews·Thomas J PenfoldChristel M Marian
Oct 7, 2017·The Journal of Physical Chemistry Letters·Jacob A BerenbeimMattanjah S de Vries
Aug 30, 2017·The Journal of Physical Chemistry Letters·Brennan AshwoodCarlos E Crespo-Hernández
Aug 3, 2017·The Journal of Physical Chemistry Letters·Andrew J Atkins, Leticia González
Dec 14, 2018·The Journal of Physical Chemistry. B·Panwang Zhou, Li Zhao
Sep 27, 2018·The Journal of Physical Chemistry. a·Hiromi NakaiQi Wang

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