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Photochromic and Reductive Electrochemical Switching of a Dithiazolylethene with Large Redox Modulation
Author(s) -
Léaustic Anne,
AnxolabéhèreMallart Elodie,
Maurel François,
Midelton Stéphanie,
Guillot Régis,
Métivier Rémi,
Nakatani Keitaro,
Yu Pei
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002451
Subject(s) - photochromism , redox , electrochemistry , modulation (music) , reduction (mathematics) , materials science , chemistry , photochemistry , electrode , inorganic chemistry , physics , mathematics , geometry , acoustics
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 .