title: Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources.
abstract: In this paper, we present a novel concept for "smarter" photolabile organic compounds combining not one but two caged functions. As proof of principle, this diarylethene-based compound possesses two inhibited chemical groups (OMe and OAc) and its efficient release in different solvents is reported. In low- to medium-polarity media, both MeOH and AcOH are released, with a slight preferential uncaging of AcOH except in 1,4-dioxane, where MeOH is preferentially released. In contrast, DMSO or DMF render AcOH release strongly dominating. DFT calculations of the corresponding photoreactive conformations not only afford strong support to the observed release of MeOH and AcOH but also qualitatively explain the preferential release of acid in terms of dispersive noncovalent interactions. Finally, mechanistic aspects are discussed on the bases of the spectroscopic observations and of the TD-DFT calculations.
authors.affiliation: International Collaborative Laboratory for Supraphotoactive Systems, NAIST-CEMES, CNRS UPR 8011 , 29 rue Marvig, F-31055 Toulouse Cedex 4, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Galangau
authors.affiliation: Université de Lille , CNRS UMR 8516 LASIR, 3, rue Pr. Laguesse, BP 83, 59006 Lille Cedex, France.
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Delbaere
authors.affiliation: International Collaborative Laboratory for Supraphotoactive Systems, NAIST-CEMES, CNRS UPR 8011 , 29 rue Marvig, F-31055 Toulouse Cedex 4, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Ratel-Ramond
authors.affiliation: International Collaborative Laboratory for Supraphotoactive Systems, NAIST-CEMES, CNRS UPR 8011 , 29 rue Marvig, F-31055 Toulouse Cedex 4, France.|Université de Toulouse , UPS, 29 rue Marvig, F-31055 Toulouse Cedex 4, France.
authors.forename: Gwénaël
authors.initials: G
authors.lastname: Rapenne
authors.affiliation: Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST , 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
authors.forename: Ruiji
authors.initials: R
authors.lastname: Li
authors.affiliation: International Collaborative Laboratory for Supraphotoactive Systems, NAIST-CEMES, CNRS UPR 8011 , 29 rue Marvig, F-31055 Toulouse Cedex 4, France.|Université de Toulouse , UPS, 29 rue Marvig, F-31055 Toulouse Cedex 4, France.|Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST , 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
authors.forename: Jan Patrick Dela Cruz
authors.initials: JP
authors.lastname: Calupitan
authors.affiliation: Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST , 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Nakashima
authors.affiliation: International Collaborative Laboratory for Supraphotoactive Systems, NAIST-CEMES, CNRS UPR 8011 , 29 rue Marvig, F-31055 Toulouse Cedex 4, France.|Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST , 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Kawai