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Oxidative Electrochemical Switching in Dithienylcyclopentenes, Part 2: Effect of Substitution and Asymmetry on the Efficiency and Direction of Molecular Switching and Redox Stability
Author(s) -
Browne Wesley R.,
de Jong Jaap J. D.,
Kudernac Tibor,
Walko Martin,
Lucas Linda N.,
Uchida Kingo,
van Esch Jan H.,
Feringa Ben L.
Publication year - 2005
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.200500163
Subject(s) - electrochemistry , ring (chemistry) , chemistry , cyclopentene , redox , moiety , intermolecular force , photochemistry , electron transfer , triad (sociology) , crystallography , stereochemistry , electrode , inorganic chemistry , molecule , organic chemistry , catalysis , psychology , psychoanalysis
The electrochemical and spectroelectrochemical properties of a series of C5‐substituted dithienylhexahydro‐ and dithienylhexafluorocyclopentenes are reported. The effect of substitution at C5 of the thienyl moiety on the redox properties is quite dramatic, in contrast to the effect on their photochemical properties. The efficiency of electrochemical switching is dependent both on the central cyclopentene unit and on the nature of the substituents, whereby electron‐donating moieties favour oxidative electrochemical ring‐closure and vice versa. Asymmetrically substituted dithienylcyclopentenes were investigated to explore the ring‐closure process in more detail. The results indicate that electrochemically induced ring‐closure occurs via the monocation of the open form. In the presence of electroactive groups at C5 of the thienyl ring (e.g., methoxyphenyl) initial oxidation of these groups is followed by intermolecular electron transfer, which drives ring‐closure of the open forms.