title: Second-Order Nonlinear Optical Properties of a Dithienylethene-Indolinooxazolidine Hybrid: A Joint Experimental and Theoretical Investigation.
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.
authors.affiliation: Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, 33405 Talence Cedex (France).
authors.forename: Flavie
authors.initials: F
authors.lastname: Bondu
authors.affiliation: University of Namur, Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, rue de Bruxelles, 61, 5000 Namur (Belgium).
authors.forename: Jean
authors.initials: J
authors.lastname: Quertinmont
authors.affiliation: Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, 33405 Talence Cedex (France).
authors.forename: Vincent
authors.initials: V
authors.lastname: Rodriguez
authors.affiliation: Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, 33405 Talence Cedex (France).
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Pozzo
authors.affiliation: University of Namur, Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, rue de Bruxelles, 61, 5000 Namur (Belgium).
authors.forename: Aurélie
authors.initials: A
authors.lastname: Plaquet
authors.affiliation: University of Namur, Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, rue de Bruxelles, 61, 5000 Namur (Belgium).
authors.forename: Benoît
authors.initials: B
authors.lastname: Champagne
authors.affiliation: Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, 33405 Talence Cedex (France). frederic.castet@u-bordeaux.fr.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Castet
keywords: chromophores; hyper-Rayleigh scattering; molecular switches; nonlinear optics; quantum chemistry calculations