In this work, two newly substituted polyalkylthiophenes, poly(3,4-dihexyl-2
,2'-bithiophene) and its didodecyl analogue have been prepared in order to
compare their properties with those of the regioisomeric poly(3-alkylthioph
ene)s containing the same amount of head-to-tail configuration (conventiona
l PATs). Remarkable differences between the material characteristics of the
se two kinds of polyalkylthiophene have been observed, thus enabling us to
elucidate the side chains effects exclusively attributable to the differenc
e between the side chains distribution along the polythiophene backbone. In
the neutral bulk state, compared to that of the conventional PATs, the pol
ymers prepared for this study have been found more thermostable materials e
xhibiting higher flexibility and less ordered (in the crystallographic sens
e) molecular assemblies, still able to afford an average conjugation length
as long as that of the conventional PATs, but varying between wider limits
. This seems to be closely connected with a lower degree of side chains int
eractions and/or the high proportion (50%) of unsubstituted thiophene rings
. Based on these effects of molecular structure on the material properties
at room temperature, we have anticipated in the novel polymers, at higher t
emperatures, the possibility of weaker thermochromism and better conductivi
ty stability than in their regioisomeric conventional PATs. (C) 2000 Elsevi
er Science Ltd. All rights reserved.