Second‐Order Nonlinear Optical Properties of a Dithienylethene–Indolinooxazolidine Hybrid: A Joint Experimental and Theoretical Investigation |
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Authors: | Dr Flavie Bondu Jean Quertinmont Prof?Dr Vincent Rodriguez Prof?Dr Jean‐Luc Pozzo Dr Aurélie Plaquet Prof?Dr Benoît Champagne Prof?Dr Frédéric Castet |
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Institution: | 1. Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, 33405 Talence Cedex (France);2. University of Namur, Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, rue de Bruxelles, 61, 5000 Namur (Belgium) |
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Abstract: | The nonlinear optical (NLO) properties of a double photochrome molecular switch are reported for the first time by considering the four trans forms of a dithienylethene–indolinooxazolidine hybrid. The four forms are characterized by means of hyper‐Rayleigh scattering (HRS) experiments and quantum chemical calculations. Experimental measurements provide evidence that the pH‐ and light‐triggered transformations between the different forms of the hybrid are accompanied by large variations of the first hyperpolarizability, which makes this compound an effective multistate NLO switch. Quantum chemical calculations conducted at the time‐dependent Hartree–Fock and time‐dependent DFT levels agree with the experimental data and allow a complete rationalization of the NLO responses of the different forms. The HRS signal of the forms with an open indolinooxazolidine moiety are more than one order of magnitude larger than that measured for the other forms, whereas the open/closed status of the dithienylethene subunit barely influences the dynamic NLO properties. However, extrapolation of the NLO responses to the static limit leads to univocally distinguishable intrinsic responses for three of the various forms. This hybrid system thus acts as a highly efficient multistate NLO switch for eventual exploitation in optical memory systems with multiple storage and nondestructive readout capacity. |
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Keywords: | chromophores hyper‐Rayleigh scattering molecular switches nonlinear optics quantum chemistry calculations |
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