The development of new semiconducting conjugated polymers has been an important
aspect of plastic electronics research since the early days of the field, as it allows the
optoelectronic properties to be tuned for various applications. Dithienometalloles, which
consist of a 2,2’-bithiophene fused with a bridging heteroatom, have been an important class of
monomers for some time. The heteroatom serves an important role, both in holding the
bithiophene unit rigidly coplanar and also in tuning the energetics of the system. In addition,
these moieties often possess alkyl chains located on the bridging heteroatom that serve to
confer solubility and processability to the final polymers.
In this thesis we report the synthesis and properties of a number of dithienometallolecontaining
polymers, in which the necessary solubilising groups have been moved from the
bridging heteroatom to the adjacent thiophene backbone of the dithienometallole. This enabled
the preparation of novel, soluble arsole-containing conjugated polymers. These dithienoarsole containing
materials were used in both organic field effect transistors and organic photovoltaic
devices, showing promising performances as well as significantly improved air stability over
their phosphorus-containing analogues. The effect of changing the bridging heteroatom in
dithienometalloles was also studied by comparing the optoelectronic properties and device
performances of polymers with carbonyl, silicon, germanium, and nitrogen bridging groups.
Finally, dithienopyrrole-based sensors were developed that showed substantial colour changes
on exposure to basic solutions, as well as potential for use as readily dopable materials for
electronic applications.