Four new disubstituted propylenedioxythiophene polymers have been synthesized by
Grignard metathesis on the 1−5 g scale. All polymers were found to be soluble in chloroform, methylene
chloride, toluene, and tetrahydrofuran and were fully structurally characterized having GPC determined
number-average molecular weights ranging from 33000 to 47000 g mol-1. Dilute polymer solutions in
toluene exhibited strong red fluorescence with moderate quantum efficiencies from 0.38 to 0.50.
Homogeneous thin films were formed by electropolymerization and spray casting polymer solutions onto
ITO coated glass slides at thicknesses of ca. 150 nm. The films were electroactive, switching from a dark
blue-purple to a transmissive sky blue upon p-doping, often with subsecond switching times, and high
electrochromic contrast luminance changes (% ΔY) of 40−70%. These studies revealed that the branched
derivatives, [poly(3,3-bis(2-ethylhexyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)] and [poly(6,8-dibromo-3,3-bis(2-ethylhexyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)], gave an electrochemical response and associated color change over a much smaller voltage range in comparison to the linear chain
substituted derivatives, [poly(3,3-dihexyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)] and [poly(3,3-bis(octadecyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)]. Composite coloration efficiency values
were found up to 1365 cm2/C; this was considerably larger than values obtained from previously studied
alkylenedioxythiophene based polymers (∼375 cm2/C).