Optomechanical Control of Quantum Yield in Trans–Cis Ultrafast Photoisomerization of a Retinal Chromophore Model
- Valentini, A. 23
- Rivero, D. 2
- Zapata, F. 2
- García-Iriepa, C. 12
- Marazzi, M. 67
- Palmeiro, R. 2
- Fdez. Galván, I. 5
- Sampedro, D. 1
- Olivucci, M. 348
- Frutos, L.M. 2
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1
Universidad de La Rioja
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2
Universidad de Alcalá
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3
Università degli Studi di Siena
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4
Bowling Green State University
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5
Uppsala University
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6
Centre National de la Recherche Scientifique
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7
University of Lorraine
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8
University of Strasbourg
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ISSN: 1433-7851
Any de publicació: 2017
Volum: 56
Número: 14
Pàgines: 3842-3846
Tipus: Article
Altres publicacions en: Angewandte Chemie International
Resum
The quantum yield of a photochemical reaction is one of the most fundamental quantities in photochemistry, as it measures the efficiency of the transduction of light energy into chemical energy. Nature has evolved photoreceptors in which the reactivity of a chromophore is enhanced by its molecular environment to achieve high quantum yields. The retinal chromophore sterically constrained inside rhodopsin proteins represents an outstanding example of such a control. In a more general framework, mechanical forces acting on a molecular system can strongly modify its reactivity. Herein, we show that the exertion of tensile forces on a simplified retinal chromophore model provokes a substantial and regular increase in the trans-to-cis photoisomerization quantum yield in a counterintuitive way, as these extension forces facilitate the formation of the more compressed cis photoisomer. A rationale for the mechanochemical effect on this photoisomerization mechanism is also proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim