Cs. Velazquez et Rw. Murray, SYNTHESIS AND VOLTAMMETRY OF A TETRATHIAFULVALENE POLYMER ELECTROLYTEMELT, Journal of electroanalytical chemistry [1992], 396(1-2), 1995, pp. 349-357
The synthesis and electrochemical properties are described for a tetra
thiafulvalene derivative with -S(CH2CH2O)(3)CH3 oligomers attached at
each of its four corners (TTF[E(3)M](4)). This material is a molecular
melt at room temperature and will dissolve LiClO4 as a polymer electr
olyte. Its radical cation salt, {TTF[E(3)M](+)(4)}{CF3SO3-}, is also a
room temperature melt in which LiClO4 is soluble. Microelectrode volt
ammetry in LiClO4 + TTF[E(3)M(4)] and in {TTF[E(3)M](+)(4)}{CF3SO3-} s
hows that the self-diffusivities of these TTF derivatives in their mel
ts are quite small and have room temperature values ranging from 8 X 1
0(-9) to 5 X 10(-12) cm(2) s(-1) depending on the LiClO4 content. The
experimental diffusion coefficients derived from voltammetric waves fo
r the TTF[E(3)M](0/+)(4) couple are larger than those for the TTF[E(3)
M](+/2+)(4) couple by factors ranging from 2.5 to 13, a difference not
understandable by migration effects alone. Consideration of coupling
of homogeneous TTF[E(3)M](0/+)(4) electron self-exchange to diffusion
during TTF[E(3)M](+)(4) reduction or TTF[E(3)M](4) oxidation leads to
estimation of k(EX,1/0) values in the 10(5) M(-1) s(-1) range and whic
h increase with temperature and decrease with the addition of LiClO4 e
lectrolyte.