New poly(
N-substituted di
thieno[3,2-
b:2',3'-
d]pyrrole)s (PDTPs) wi
th high molecular weights, goodyields, and increased solubility were prepared, and
their supramolecular behavior was studied. The polymersdiffer in
their polymerization me
thod (using chemical oxidants, Stille-couplings, or a Yamamoto-type polymerization) and
the bulkiness of
the side chain. The solubility of
the polymer depends on
the bulkiness of
the sidechains employed, while
the yield and, to a lesser extent,
the molecular weight depend on
the polymerizationme
thod. In general, Stille-couplings proved to be
the best polymerization me
thod for PDTPs. The higher molecularweight polymers showed more defined voltammograms, higher
max toge
ther wi
th the presence of a vibronicfine-structure, and higher fluorescence yields
than lower molecular weight materials. In solution,
the polymersare present as highly conjugated rigid rods, which, upon transition to films or in nonsolvents, poorly aggregate.The stacking is more complicated in high molecular weight polymers
than in low molecular weight samples.