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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université Paris Diderot - Paris France

   
 
Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie
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Université Paris Diderot
Université de Paris CNRS, Centre National de la Recherche Scientifique
 
 


Le LEM - Publications: Abstracts

Publication 678

Chem. Eur. J., 17 (7), 2246 - 2255, 2011
DOI: 10.1002/chem.201002451
 

doi

Photochromic and reductive electrochemical switching of a dithiazolylethene with large redox modulations

Anne Léaustic, Elodie Anxolabéhère-Mallart, François Maurel,Stéphanie Midelton, Régis Guillot, Rémi Métivier, Keitaro Nakatani, Pei Yu

ICMMO, CNRS UMR 8182, Université Paris Sud 11, Bât. 420, 91405 Orsay Cedex, France - Laboratoire d’Electrochimie Moléculaire, UMR CNRS 7591, Université Paris Diderot, 15 rue Jean-Antoine de Baïf, 75205 Paris Cedex 13, France - ITODYS, CNRS UMR 7086, Université Paris Diderot-Paris 7, 15 rue Jean-Antoine de Baïf, 75205 Paris Cedex 13, France-Laboratoire de Photophysique et de Photochimie Supramoléculaires et Macromoléculaires, CNRS UMR 8531, Ecole Normale Supérieure de Cachan, 61 avenue du Président Wilson, 94235 Cachan Cedex, France.


A new dipyridylthiazolylethene (1 a) and its dicationic analogue (2 a), with two N-methylated pyridyl rings, have been synthesized and structurally characterized. Due to the N-methylation of the pyridyl rings, 2 a displays not only very different photochromic properties, but also undergoes a reductive ring-closing reaction to generate its closed-ring isomer 2 b. Careful electrochemical studies coupled with EPR spectroscopy show that this reductive ring-closing reaction takes place when 2 a is two-electron reduced. DFT calculations suggest that such a ground-state electrocyclization is driven by a very large stabilization of the reduced closed-ring isomer 2 b relative to the reduced open-ring isomer 2 a. In addition, 2 b exhibits two successive and reversible one-electron reductions at half-wave potentials of 0.04 and −0.14 V versus SCE and a redox modulation as large as 1 V is achieved when passing from 2 a to 2 b.

 
   
 
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