Electron exchange in conformationally restricted donor-spacer-acceptor dyads: angle dependence and involvement of upper-lying excited States

Chemistry : a European Journal
Andrew C BennistonCraig A Sams

Abstract

The rate constant for triplet energy transfer (k(TET)) has been measured in fluid solution for a series of mixed-metal Ru-Os bis(2,2':6',2''-terpyridine) complexes built around a tethered biphenyl-based spacer group. The length of the tether controls the central torsion angle for the spacer, which can be varied systematically from 37 to 130 degrees . At low temperature, but still in fluid solution, the spacer adopts the lowest-energy conformation and k(TET) shows a clear correlation with the torsion angle. A similar relationship holds for the inverse quantum yield for emission from the Ru-terpy donor. Triplet energy transfer is more strongly activated at higher temperature and the kinetic data require analysis in terms of two separate processes. The more weakly activated step involves electron exchange from the first-excited triplet state on the Ru-terpy donor and the size of the activation barrier matches well with that calculated from spectroscopic properties. The pre-exponential factor derived for this process correlates remarkably well with the torsion angle and there is a large disparity in electronic coupling through pi and sigma orbitals on the spacer. The more strongly activated step is attributed to electron exchange f...Continue Reading

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Citations

May 15, 2015·The Journal of Physical Chemistry. a·Luisa G HeinzOliver S Wenger
Sep 17, 2009·Journal of the American Chemical Society·Anthony HarrimanRaymond Ziessel
Jan 29, 2010·Journal of the American Chemical Society·Troy E Knight, James K McCusker
Apr 2, 2009·Journal of the American Chemical Society·Martin WolffsAlbertus P H J Schenning
Jul 30, 2010·Journal of the American Chemical Society·Youhei YamamotoOsamu Ishitani
Mar 18, 2009·Chemistry : a European Journal·Anthony HarrimanRaymond Ziessel
May 28, 2010·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·René M Williams
Jun 17, 2010·Physical Chemistry Chemical Physics : PCCP·Bo Albinsson, Jerker Mårtensson
Oct 20, 2010·Chemical Communications : Chem Comm·Raymond Ziessel, Anthony Harriman
Jul 20, 2019·Physical Chemistry Chemical Physics : PCCP·Betül KüçüközBo Albinsson
Jan 8, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Miguel A EsteruelasMarta Valencia
Apr 25, 2013·Chemistry : a European Journal·Marek B MajewskiMichael O Wolf
Oct 14, 2008·Journal of the American Chemical Society·Youhei YamamotoOsamu Ishitani
Dec 23, 2009·Nano Letters·Artem MishchenkoThomas Wandlowski

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