Spectral Tuning and Photoisomerization Efficiency in Push–Pull Azobenzenes: Designing Principles
| Autor: | Luca Salvigni, Lorenzo Montali, Alessia Ventimiglia, Irene Conti, Flavia Aleotti, Giuseppe Cirillo, Andrea Giunchi, Mohsen M. T. El-Tahawy, Matteo Bonfanti, Stefano Scurti, Claudia Spallacci, Marziogiuseppe Gentile, Artur Nenov, Marco Garavelli |
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| Přispěvatelé: | Aleotti F., Nenov A., Salvigni L., Bonfanti M., El-Tahawy M.M., Giunchi A., Gentile M., Spallacci C., Ventimiglia A., Cirillo G., Montali L., Scurti S., Garavelli M., Conti I. |
| Rok vydání: | 2020 |
| Předmět: |
Work (thermodynamics)
Push-Pull Azobenzenes Spectral Tuning Photoisomerization 010304 chemical physics Photoisomerization Quantum yield Bending 010402 general chemistry 01 natural sciences Potential energy Article 0104 chemical sciences chemistry.chemical_compound Azobenzene chemistry Chemical physics 0103 physical sciences Density functional theory Physical and Theoretical Chemistry Isomerization |
| Zdroj: | The Journal of Physical Chemistry A The Journal of Physical Chemistry. a |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.0c08672 |
| Popis: | This work demonstrates how push-pull substitution can induce spectral tuning toward the visible range and improve the photoisomerization efficiency of azobenzene-based photoswitches, making them good candidates for technological and biological applications. The red-shifted bright ππ∗ state (S2) behaves like the lower and more productive dark nπ∗ (S1) state because less potential energy along the planar bending mode is available to reach higher energy unproductive nπ*/S0 crossing regions, which are responsible for the lower quantum yield of the parent compound. The stabilization of the bright ππ∗ state and the consequent increase in isomerization efficiency may be regulated via the strength of push-pull substituents. Finally, the torsional mechanism is recognized here as the unique productive route because structures with bending values attributable to the inversion mechanism were never detected, out of the 280 ππ∗ time-dependent density functional theory (RASPT2-validated) dynamics simulations. |
| Databáze: | OpenAIRE |
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