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Persistent Mixed‐Valence [(TTF) 2 ] +. Dyad of a Chiral Bis(binaphthol)–tetrathiafulvalene (TTF) Derivative
Author(s) -
Saad Ali,
Barrière Frédéric,
Levillain Eric,
Vanthuyne Nicolas,
Jeannin Olivier,
Fourmigué Marc
Publication year - 2010
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.200902050
Subject(s) - tetrathiafulvalene , enantiopure drug , valence (chemistry) , diastereomer , enantiomer , chemistry , valence bond theory , electrochemistry , molecule , stereochemistry , crystallography , molecular orbital , enantioselective synthesis , organic chemistry , electrode , catalysis
Mixed‐valence dyadic [(TTF) 2 ] +. (TTF=tetrathiafulvalene) species—the elementary building blocks of organic conductors—are usually too weakly associated to be observed in solution, unless covalently bound in dimers or physically constrained into a cage structure. We demonstrate here that a novel chiral tetrathiafulvalene functionalised with two 1,1′‐binaphthol units ( 1 ) is able to associate in solution into persistent mixed‐valence [(TTF) 2 ] +. dyadic moieties through a stereospecific recognition pattern. This redox active molecule exhibits different electrochemical and spectroscopic responses, as enantiopure RR , SS or meso isomers, a rare example of a chiral system in which different diastereoisomers do not exhibit the same electrochemical features, with a selective formation of the mixed‐valence species in the enantiopure ( RR )‐ 1 or ( SS )‐ 1 isomers only, whereas the meso form does not show this association ability. A rationale for the selective self‐association of the RR and SS enantiomers upon oxidation is provided, based on the different molecular geometries and accessibility of the TTF core toward the formation of the mixed‐valence species.