S. Akoudad et al., Low oxidation potential tetrathiafulvalene analogues based on 3,4-dialkoxythiophene pi-conjugating spacers, J ORG CHEM, 64(12), 1999, pp. 4267-4272
Tetrathiafulvalene analogues involving dihexyloxythiophene (1), ethylenedio
xythiophene (2), and bis(3,4-dihexyloxy-2-thienyl)ethylene (3) as conjugati
ng spacer and diversely substituted at the 1,3-dithiole ring (R) have been
synthesized. Electronic absorption spectra show the expected decrease of HO
MO-LUMO gap when increasing the electron-releasing power of R or the length
of the conjugating spacer. Cyclic voltammetry (CV) shows that whereas comp
ounds 1 and 2 are reversibly oxidized into their cation radical and dicatio
n through two one-electron steps, for compounds 3 the dication is formed di
rectly via a two-electron transfer. Comparison of the data for compounds 2
and 3 with those of their respective analogues based on thiophene and dithi
enylethylene shows that introduction of the electron-donating alkoxy groups
at the 3 and 4 positions of the thiophene ring produces a 150-200 mV negat
ive shift of the first redox potential (E degrees(1)). On the other hand, C
V data for compounds 1 and 2 reveal several unusual features such as E degr
ees(1) approximate to 0.10 V/SCE ranking among-the lowest known to date and
a Coulombic repulsion between positive charges in the dication larger than
for the analogue ct-donors based on unsubstituted thiophene. These results
are interpreted by a major reorganization of the electronic distribution i
n the donor molecule due to alkoxy groups: the highest electron density mov
ing from the 1,3-dithiole moiety toward the central thiophene ring.