title: Cooperative Veratryle and Nitroindoline Cages for Two-Photon Uncaging in the NIR.
abstract: Tandem uncaging systems in which a two-photon absorbing module and a cage moiety, linked via a phosphorous clip, that act together by Förster resonance energy transfer (FRET) have been developed. A library of these compounds, using different linkers and cages (7-nitroindolinyl or nitroveratryl) has been synthesized. The investigation of their uncaging and two-photon absorption properties demonstrates the scope and versatility of the engineering strategy towards efficient two-photon cages and reveals surprising cooperative and topological effects. The interactions between the 2PA module and the caging moiety are found to promote cooperative effects on the 2PA response while additional processes that enhance the uncaging efficiency are operative in well-oriented nitroindoline-derived dyads. These synergic effects combine to lead to record two-photon uncaging cross-section values (i.e., up to 20 GM) for uncaging of carboxylic acids.
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Eduardo
authors.initials: E
authors.lastname: Cueto Diaz
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Picard
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Maxime
authors.initials: M
authors.lastname: Klausen
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Hugues
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Paolo
authors.initials: P
authors.lastname: Pagano
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France.
authors.forename: Emilie
authors.initials: E
authors.lastname: Genin
authors.affiliation: University of Bordeaux, Institut des Sciences Moléculaires (UMR5255 CNRS), 351 cours de la liberation, 33450, Talence, France. mireille.blanchard-desce@u-bordeaux.fr.
authors.forename: Mireille
authors.initials: M
authors.lastname: Blanchard-Desce
keywords: Förster resonance energy transfer; caged compounds; photolysis; two-photon absorption; two-photon uncaging