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A Multifunctional Photoswitch: 6π Electrocyclization versus ESIPT and Metalation |
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| Authors: | Dr. Juliette Guérin Dr. Anne Léaustic Prof. Stéphanie Delbaere Dr. Jérôme Berthet Dr. Régis Guillot Dr. Cyril Ruckebusch Dr. Rémi Métivier Prof. Keitaro Nakatani Dr. Maylis Orio Dr. Michel Sliwa Dr. Pei Yu |
| Affiliation: | 1. Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182, Université Paris‐Sud, Bat. 420, 91405 Orsay Cedex (France), Fax: (+33)?169‐15‐4754;2. Université Lille Nord de France, UDSL, CNRS UMR 8516, 3, rue du Professeur Laguesse, 59006 Lille cedex (France);3. Laboratoire de Spectrochimie Infrarouge et Raman (LASIR), CNRS UMR 8516/Université Lille Nord de France, Université Lille1 ‐ Sciences et Technologies/Chemistry Department bat C5/59655 Villeneuve d'Ascq Cedex (France), Fax: (+33)?320‐43‐6755;4. PPSM, ENS Cachan, UMR 8531, 61 av. Président Wilson, 94235 Cachan cedex (France) |
| Abstract: | A terthiazole‐based molecular switch associating 6π electrocyclization, excited state intramolecular proton transfer (ESIPT), and strong metal binding capability was prepared. The photochemical and photophysical properties of this molecule and of the corresponding nickel and copper complexes were thoroughly investigated by steady‐state and ultrafast absorption spectroscopy and rationalized by DFT/TDDFT calculations. The switch behaves as a biphotochrome with time‐dependent photochemical outcome and displays efficient ESIPT‐based fluorescence photoswitching. Both photochemical reactions are suppressed by nickel or copper metalation, and the main factors contributing to the quenching of the electrocyclization are discussed. |
| Keywords: | density functional calculations femtosecond chemistry intramolecular proton transfer metalation photochromism |