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The primary steps in excited-state hydrogen transfer: the phototautomerization of o-nitrobenzyl derivatives.
Journal article

The primary steps in excited-state hydrogen transfer: the phototautomerization of o-nitrobenzyl derivatives.

  • 2014-05-16
Published in:
  • Chemistry (Weinheim an der Bergstrasse, Germany). - 2014
Bell-Evans-Polanyi principle
hydrogen transfer
photochemistry
quantum chemical calculations
reaction mechanisms
English The quantum yield for the release of leaving groups from o-nitrobenzyl "caged" compounds varies greatly with the nature of these leaving groups, for reasons that have never been well understood. We found that the barriers for the primary hydrogen-atom transfer step and the efficient nonradiative processes on the excited singlet and triplet surfaces determine the quantum yields. The excited-state barriers decrease when the exothermicity of the photoreaction increases, in accord with Bell-Evans-Polanyi principle, a tool that has never been applied to a nonadiabatic photoreaction. We further introduce a simple ground-state predictor, the radical-stabilization energy, which correlates with the computed excited-state barriers and reaction energies, and that might be used to design new and more efficient photochemical processes.
Language
  • English
Open access status
closed
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Persistent URL
https://folia.unifr.ch/global/documents/242105
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