10.1021/jo0009649.s001
Rafael Gómez
Rafael
Gómez
José L. Segura
José L.
Segura
Nazario Martín
Nazario
Martín
New Chiral Binaphthyl Building Blocks: Synthesis of the First
Optically Active Tetrathiafulvalene and
11,11,12,12-Tetracyano-9,10-anthraquinodimethane Dimers<sup>†</sup>
American Chemical Society
2000
dimers
TTF
PM
naphthalene moiety
electroactive units
TCAQ
binaphthyl derivatives
binaphthyl systems ranges
2000-10-07 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/New_Chiral_Binaphthyl_Building_Blocks_Synthesis_of_the_First_Optically_Active_Tetrathiafulvalene_and_11_11_12_12-Tetracyano-9_10-anthraquinodimethane_Dimers_sup_sup_/3686421
New enantiomerically pure binaphthyl derivatives bearing triphenylphosphine or phosphonate
groups have been synthesized and used as building blocks to prepare the first optically active TTF
and TCAQ dimers. Due to the restricted rotation of the two naphthalene rings, binaphthyl
derivatives are ideal candidates to be used as nonplanar spacers between electroactive units in
the search for materials with enhanced dimensionality. The electronic absorption spectra of dimers
in which the electroactive unit is in conjugation with the naphthalene fragment reveal the presence
of intramolecular photoinduced electron-transfer process from the TTF to the naphthalene unit in
<b>5</b> and <b>6</b> and from the naphthalene moiety to the TCAQ unit in <b>7</b>. Electrochemical studies on the
new dimers show the redox potentials of TTF and TCAQ units as well as the oxidation wave for
the naphthalene moiety and reveal no significant electronic interaction between the two electroactive
units, which is in agreement with the results obtained from theoretical calculations at the PM-3
level which indicate that the angle between rings in the binaphthyl systems ranges from 75 to 80°.