Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2 (dppz)]2+ light-switch compound in solution and when bound to DNA

Chemical Science
Fergus E PoyntonJohn M Kelly

Abstract

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this "light-switch" effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280-1450 cm-1, which characterise both the emissive "bright" and the non-emissive "dark" excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the "dark" excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the "bright" state are observed for both Λ- and Δ-enantiomers of 1 when bound to...Continue Reading

References

Jul 11, 1980·Nucleic Acids Research·A A Maevsky, B I Sukhorukov
Dec 1, 1986·Physical Review A: General Physics·W YangC Lee
Sep 15, 1988·Physical Review A: General Physics·A D Becke
May 17, 2000·Proceedings of the National Academy of Sciences of the United States of America·B OnfeltA H Zewail
Mar 12, 1997·Inorganic Chemistry·Rajesh B. NairCatherine J. Murphy
Oct 24, 2001·Inorganic Chemistry·Kristin M. OmbergThomas J. Meyer
Dec 12, 2002·Journal of the American Chemical Society·Matthew K BrennamanJohn M Papanikolas
Jul 25, 2003·Biophysical Chemistry·Martina BanyayAstrid Gräslund
Jan 15, 2004·Journal of the American Chemical Society·Geoffrey PourtoisJean-Luc Brédas
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Feb 3, 2007·Science·Wolfgang J SchreierBern Kohler
Feb 24, 2010·The Journal of Physical Chemistry. B·Anthony W ParkerMarina K Kuimova
May 18, 2010·Biophysical Chemistry·Frida R SvenssonPer Lincoln
Oct 5, 2011·Proceedings of the National Academy of Sciences of the United States of America·James P HallChristine J Cardin
Jan 29, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrew W McKinleyEimer M Tuite
Jul 13, 2013·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Nancherla DeepikaSirasani Satyanarayana
Jul 24, 2013·Journal of the American Chemical Society·James P HallChristine J Cardin
Nov 2, 2013·Journal of Photochemistry and Photobiology. B, Biology·Guang-Bin JiangYun-Jun Liu
Nov 15, 2013·Chemical Communications : Chem Comm·Erin WachterEdith C Glazer
Mar 13, 2014·Proceedings of the National Academy of Sciences of the United States of America·Dominik B BucherWolfgang Zinth
Aug 26, 2014·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Bing-Jie HanYun-Jun Liu
Sep 13, 2014·Chemistry : a European Journal·Cristina MariGilles Gasser
Mar 24, 2015·Accounts of Chemical Research·Stephen D Fried, Steven G Boxer
Aug 26, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Gary J RyanThorfinnur Gunnlaugsson
Oct 23, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Xing GaoTian-Ming Yao
Nov 13, 2015·Chemistry : a European Journal·Erin WachterEdith C Glazer

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Citations

Oct 18, 2018·Chemistry : a European Journal·Shu YangQianfan Yang
Feb 21, 2018·Nature Chemistry·B DickeS Herres-Pawlis
Jul 19, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Guanying LiHui Chao
Oct 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Nenad JoksimovićNenad Janković
Jan 21, 2017·Chemistry : a European Journal·James P HallChristine J Cardin
Nov 1, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Bjørn C PoulsenThorfinnur Gunnlaugsson
Nov 28, 2017·Chemical Society Reviews·Fergus E PoyntonThorfinnur Gunnlaugsson
May 19, 2017·Physical Chemistry Chemical Physics : PCCP·Francesco NastasiMaurizio Prato
Nov 1, 2016·Journal of Fluorescence·Quentin DeraedtBenjamin Elias
Jul 29, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Jasmine M CrossJames W Walton
Jan 31, 2021·Physical Chemistry Chemical Physics : PCCP·Christopher B Larsen
Feb 24, 2021·Inorganic Chemistry·Jérôme TisaunCécile Moucheron
Jul 20, 2018·The Journal of Physical Chemistry. a·Julian SchindlerBenjamin Dietzek
Dec 21, 2017·Journal of the American Chemical Society·Tyler J WhittemoreClaudia Turro

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Methods Mentioned

BETA
X-ray
NMR
gel filtration

Software Mentioned

SHELXL
ps
Gaussian

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