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Optomechanical Control of Quantum Yield in Trans – Cis Ultrafast Photoisomerization of a Retinal Chromophore Model
Author(s) -
Valentini Alessio,
Rivero Daniel,
Zapata Felipe,
GarcíaIriepa Cristina,
Marazzi Marco,
Palmeiro Raúl,
Fdez. Galván Ignacio,
Sampedro Diego,
Olivucci Massimo,
Frutos Luis Manuel
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201611265
Subject(s) - photoisomerization , chromophore , quantum yield , retinal , chemistry , photochemistry , quantum , steric effects , rhodopsin , isomerization , chemical physics , physics , stereochemistry , quantum mechanics , organic chemistry , biochemistry , fluorescence , catalysis
Abstract 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.