The Primary steps in excited-state hydrogen transfer: the phototautomerization of o-nitrobenzyl derivatives
- Šolomek, Tomáš Département de chimie, Université de Fribourg, Switzerland
- Bochet, Christian G. Département de chimie, Université de Fribourg, Switzerland
- Bally, Thomas Département de chimie, Université de Fribourg, Switzerland
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23.06.2014
Published in:
- Chemistry – A European Journal. - 2014, vol. 20, no. 26, p. 8062–8067
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.
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Chimie
- Language
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- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 211409
- DOI 10.1002/chem.201303338
- Persistent URL
- https://folia.unifr.ch/unifr/documents/303668
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